TW201339754A - Colored photosensitive composition and method of producing the same, color filter and method of producing the same, and display device - Google Patents

Colored photosensitive composition and method of producing the same, color filter and method of producing the same, and display device Download PDF

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TW201339754A
TW201339754A TW101149984A TW101149984A TW201339754A TW 201339754 A TW201339754 A TW 201339754A TW 101149984 A TW101149984 A TW 101149984A TW 101149984 A TW101149984 A TW 101149984A TW 201339754 A TW201339754 A TW 201339754A
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group
pigment
dispersion
dye
photosensitive composition
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TWI591433B (en
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Akio Katayama
Shuichiro Osada
Yuuichi Fukushige
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Fujifilm Corp
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    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
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    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
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    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
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    • C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
    • C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
    • C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
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    • C09B29/363—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O) from diazotized amino carbocyclic rings
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    • C09B29/3665—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms
    • C09B29/3669—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic ring with two nitrogen atoms from a pyrimidine ring
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    • C09B67/0022—Wet grinding of pigments
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    • C09B67/0001—Post-treatment of organic pigments or dyes
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    • G02—OPTICS
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    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
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    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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Abstract

A colored photosensitive composition is provided, comprising: (A) green pigment, (B) dye which has different main skeleton from the green pigment, and (C) polymerizable compound, and more than 15% by weight of the (B) dye is adsorbed on the surface of the (A) green pigment.

Description

著色感光性組成物、彩色濾光片及其製造方法、以及顯示裝置 Coloring photosensitive composition, color filter, manufacturing method thereof, and display device

本發明是有關於一種著色感光性組成物、彩色濾光片(color filter)及其製造方法以及顯示裝置。 The present invention relates to a coloring photosensitive composition, a color filter, a method of manufacturing the same, and a display device.

製備用於製作液晶顯示裝置或固體攝像元件(電荷耦合器件(charge-coupled device，CCD)、互補金屬氧化物半導體(complementary metal-oxide semiconductor，CMOS)等)中使用的彩色濾光片的著色感光性組成物的方法之一已知有顏料分散法。 Preparation of color sensitization for producing a color filter used in a liquid crystal display device or a solid-state imaging device (charge-coupled device (CCD), complementary metal-oxide semiconductor (CMOS), etc.) One of the methods of the sexual composition is known as a pigment dispersion method.

該顏料分散法是使用使顏料分散於各種感光性組成物中而成的著色感光性組成物，利用光微影法來製作彩色濾光片的方法。該方法由於利用光微影法進行圖案化，故而被認為是適合於製作位置精度高、大畫面、高精細的彩色濾光片的方法。在利用顏料分散法來製作彩色濾光片的情況下，藉由利用旋轉塗佈機或輥塗佈機等，塗佈著色感光性組成物而形成塗膜，然後對該塗 膜進行曝光、顯影，從而形成著色圖案，對每種顏色重複進行該操作，藉此獲得彩色濾光片。著色感光性組成物例如已知含有酞花青(phthalocyanine)系顏料的彩色濾光片用綠色著色感光性組成物(例如參照日本專利第3387541號公報)。 This pigment dispersion method is a method of producing a color filter by photolithography using a colored photosensitive composition obtained by dispersing a pigment in various photosensitive compositions. Since this method is patterned by the photolithography method, it is considered to be a method suitable for producing a color filter having high positional accuracy, large screen, and high definition. When a color filter is produced by a pigment dispersion method, a colored photosensitive composition is applied by a spin coater or a roll coater to form a coating film, and then the coating film is applied. The film is exposed and developed to form a colored pattern, which is repeated for each color, thereby obtaining a color filter. For the coloring photosensitive composition, for example, a green coloring photosensitive composition for a color filter containing a phthalocyanine pigment is known (for example, refer to Japanese Patent No. 3,875,451).

近年來，對於彩色濾光片的性能要求逐漸變得嚴格，尤其重視色相、亮度。 In recent years, the performance requirements for color filters have become stricter, with particular emphasis on hue and brightness.

對應於此種狀況，先前提出有代替顏料而使用染料的技術(例如參照日本專利第3387541號公報、日本專利特開2008-292970號公報、日本專利特開2009-86375號公報)。然而，已知染料通常與顏料相比耐熱性差，為了充分發揮染料的性能而進一步謀求改良。 In response to such a situation, a technique of using a dye instead of a pigment has been proposed (for example, refer to Japanese Patent No. 3,837, 751, Japanese Patent Laid-Open No. 2008-292970, and Japanese Patent Laid-Open No. 2009-86375). However, it is known that a dye is generally inferior in heat resistance to a pigment, and further improved in order to fully exhibit the performance of the dye.

因此，亦開發出將染料與顏料併用的技術。例如提出有使用吸附有染料的顏料的水系噴墨記錄用油墨(例如參照日本專利特開平9-151344號公報及日本專利第4167053號公報)，但並不是可勝任彩色濾光片用途的技術，故而期望進一步的技術開發。另外，亦提出有利用高分子分散劑來分散顏料，製成包含未吸附於顏料表面的染料的分散組成物，使用該分散組成物來提供著色感光性組成物。(例如參照日本專利特開2011-178865號公報。) Therefore, a technique of using a dye together with a pigment has also been developed. For example, a water-based inkjet recording ink using a dye-adsorbed pigment is proposed (for example, Japanese Patent Laid-Open No. Hei 9-151344 and Japanese Patent No. 4,170,053), but it is not a technique capable of using a color filter. Therefore, further technical development is expected. Further, it has also been proposed to disperse a pigment by using a polymer dispersant to form a dispersion composition containing a dye which is not adsorbed on the surface of the pigment, and to provide a coloring photosensitive composition using the dispersion composition. (For example, refer to Japanese Laid-Open Patent Publication No. 2011-178865.)

另外，作為使用顏料及染料來製備著色感光性組成物的方法，考慮在分散有顏料的顏料分散液中直接混合粉體染料的方 法。該方法中，在組成物中的固體成分濃度高的情況或染料相對於顏料的質量比率大的情況下，若將粉體的染料直接添加於顏料分散液中，則存在如下傾向：在添加後的攪拌溶解步驟中使染料溶解於溶劑中的過程中，顏料的分散狀態變化，顏料的分散性、分散穩定性劣化。 Further, as a method of preparing a colored photosensitive composition using a pigment and a dye, a method of directly mixing a powder dye in a pigment dispersion liquid in which a pigment is dispersed is considered. law. In this method, when the solid content concentration in the composition is high or the mass ratio of the dye to the pigment is large, when the dye of the powder is directly added to the pigment dispersion liquid, there is a tendency that after the addition In the process of dissolving the dye in the solvent in the stirring and dissolving step, the dispersion state of the pigment changes, and the dispersibility and dispersion stability of the pigment are deteriorated.

另外，該方法中，亦存在作為粉體的染料的溶解需要長時間，或染料不完全溶解，或染料難以均勻混合的情況。進而，存在難以確認染料溶解等擔憂，在製造方面亦存在障礙。 Further, in this method, it is also required that the dissolution of the dye as a powder takes a long time, or the dye is not completely dissolved, or the dye is difficult to uniformly mix. Further, there is a concern that it is difficult to confirm the dissolution of the dye, and there are also obstacles in terms of production.

利用上述該些方法而獲得的著色感光性組成物無法充分對應對耐熱性高、可顯示高畫質影像的彩色濾光片的要求，故而期望進一步的改良。 The colored photosensitive composition obtained by the above methods cannot sufficiently respond to the demand for a color filter having high heat resistance and capable of displaying high-quality images, and further improvement is desired.

本發明是鑒於上述狀況而形成。即，本發明的課題在於提供一種著色感光性組成物，其在形成彩色濾光片等的著色層的情況下，可形成耐熱性良好、亮度高、且對比度高的著色層。 The present invention has been made in view of the above circumstances. That is, an object of the present invention is to provide a coloring photosensitive composition which can form a coloring layer which is excellent in heat resistance, high in brightness, and high in contrast when a coloring layer such as a color filter is formed.

另外，本發明的課題在於提供使用上述著色感光性組成物而形成，且可顯示亮度高、對比度高的影像的彩色濾光片及其製造方法，以及包括該彩色濾光片的可顯示良好畫質的的顯示裝置。 Further, an object of the present invention is to provide a color filter which is formed by using the above-described colored photosensitive composition and which can display an image having high luminance and high contrast, a method for producing the same, and a displayable good image including the color filter. Quality display device.

本發明的上述課題是由下述方法來達成。 The above object of the present invention is achieved by the following method.

〈1〉一種著色感光性組成物，包含：(A)綠色顏料、(B) 具有與上述綠色顏料不同的母骨架的染料、以及(C)聚合性化合物，並且上述(B)染料的15質量%以上吸附於上述(A)綠色顏料的表面。 <1> A colored photosensitive composition comprising: (A) a green pigment, (B) A dye having a mother skeleton different from the green pigment and (C) a polymerizable compound, and 15% by mass or more of the dye of the above (B) is adsorbed on the surface of the green pigment (A).

〈2〉如〈1〉所述的著色感光性組成物，其中包含：將上述(A)綠色顏料與上述(B)染料在同一系統內進行分散處理而獲得的分散組成物。 (2) The coloring photosensitive composition according to <1>, which comprises a dispersion composition obtained by dispersing the (A) green pigment and the (B) dye in the same system.

〈3〉如〈1〉或〈2〉所述的著色感光性組成物，其中上述分散組成物是當將分散初期的分散組成物中的上述(B)染料的濃度設為Ci，且將分散結束後的分散組成物中的上述(B)染料的濃度設為Cf時，滿足Ci>Cf的關係的分散組成物。 (3) The colored photosensitive composition according to <1> or <2>, wherein the dispersion composition is such that the concentration of the dye (B) in the dispersion composition at the initial stage of dispersion is Ci, and is dispersed. When the concentration of the dye (B) in the dispersion composition after completion is Cf, the dispersion composition satisfying the relationship of Ci>Cf is obtained.

〈4〉如〈1〉至〈3〉中任一項所述的著色感光性組成物，其中上述(B)染料是選自由下述通式(a-1)、通式(a-2)、通式(b)以及通式(c)所組成族群中的至少一者所表示的化合物： The colored photosensitive composition according to any one of <1> to <3> wherein the (B) dye is selected from the following formula (a-1) and formula (a-2) a compound represented by at least one of the group consisting of: general formula (b) and formula (c):

通式(a-1)及通式(a-2)中，R1~R5分別獨立地表示 氫原子、或者一價取代基； In the general formula (a-1) and the general formula (a-2), R 1 to R 5 each independently represent a hydrogen atom or a monovalent substituent;

通式(b)中，R6及R7分別獨立地表示氫原子、或者一價取代基；R8表示氫原子、脂肪族基、芳基、雜環基、胺甲醯基、烷氧基羰基、芳氧基羰基、醯基、烷基磺醯基、芳基磺醯基、或者胺磺醯基；Q表示重氮成分殘基；通式(b)所表示的色素可在任意位置形成二聚物以上的多聚物； In the formula (b), R 6 and R 7 each independently represent a hydrogen atom or a monovalent substituent; and R 8 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an amine formazan group, an alkoxy group. a carbonyl group, an aryloxycarbonyl group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; Q represents a diazo component residue; the pigment represented by the formula (b) can be formed at any position a polymer of a dimer or more;

通式(c)中，R9及R10分別獨立地表示氫原子、或者 一價取代基；R11表示氫原子、脂肪族基、芳基、雜環基、胺甲醯基、烷氧基羰基、芳氧基羰基、醯基、烷基磺醯基、芳基磺醯基、或者胺磺醯基，A表示重氮成分殘基。 In the formula (c), R 9 and R 10 each independently represent a hydrogen atom or a monovalent substituent; and R 11 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an amine formazan group, an alkoxy group. A carbonyl group, an aryloxycarbonyl group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, and A represents a diazo component residue.

〈5〉如〈1〉至〈4〉中任一項所述的著色感光性組成物，其中包含：將上述(A)綠色顏料與上述(B)染料預混合後，將所得的有色材料混合物分散而獲得的分散組成物。 The coloring photosensitive composition according to any one of <1> to <4> which comprises: premixing the (A) green pigment and the (B) dye, and mixing the obtained colored material. Dispersed composition obtained by dispersion.

〈6〉如〈1〉至〈5〉中任一項所述的著色感光性組成物，其中更含有(D)光聚合起始劑。 The colored photosensitive composition according to any one of <1> to <5> which further contains (D) a photopolymerization initiator.

〈7〉如〈1〉至〈6〉中任一項所述的著色感光性組成物，其中更含有(E)鹼可溶性黏合劑。 The colored photosensitive composition according to any one of <1> to <6> which further contains (E) an alkali-soluble binder.

〈8〉一種彩色濾光片，其是使用如〈1〉至〈7〉中任一項所述的著色感光性組成物來製作。 <8> A color filter produced by using the coloring photosensitive composition according to any one of <1> to <7>.

〈9〉一種彩色濾光片的製造方法，包括：著色層形成步驟，將如〈1〉至〈7〉中任一項所述的著色感光性組成物塗佈於支持體上而形成著色層；曝光步驟，將所形成的著色層曝光成圖案式樣；以及顯影步驟，將曝光後的著色層進行顯影而形成著色圖案。 <9> A method of producing a color filter, comprising: a colored layer forming step, wherein the colored photosensitive composition according to any one of <1> to <7> is applied onto a support to form a colored layer And an exposing step of exposing the formed coloring layer to a pattern pattern; and developing a step of developing the exposed coloring layer to form a colored pattern.

〈10〉一種顯示裝置，包括如〈8〉所述的彩色濾光片或者利用如〈9〉所述的製造方法而獲得的彩色濾光片。 <10> A display device comprising the color filter according to <8> or a color filter obtained by the manufacturing method according to <9>.

〈11〉一種著色感光性組成物的製造方法，其是將(A)綠色顏料、(B)具有與上述綠色顏料不同的母骨架的染料進行分 散而製備分散組成物，然後使用上述分散組成物來製備著色感光性組成物。 <11> A method for producing a colored photosensitive composition, which comprises (A) a green pigment and (B) a dye having a parent skeleton different from the green pigment described above The dispersion composition was prepared by dispersion, and then the above-mentioned dispersion composition was used to prepare a colored photosensitive composition.

〈12〉一種著色感光性組成物的製造方法，其是將(A)綠色顏料、(B)具有與上述綠色顏料不同的母骨架的染料進行混合而製備有色材料組成物，將上述有色材料組成物進行分散來製備分散組成物，然後使用上述分散組成物來製備著色感光性組成物。 <12> A method for producing a colored photosensitive composition, wherein (A) a green pigment and (B) a dye having a parent skeleton different from the green pigment are mixed to prepare a colored material composition, and the colored material is composed of the above-mentioned colored material. The dispersion was carried out to prepare a dispersion composition, and then the above-mentioned dispersion composition was used to prepare a colored photosensitive composition.

本發明中，使用綠色顏料及染料(具有與顏料不同的母骨架)作為著色劑，在綠色顏料的表面吸附染料的一部分，藉此推測綠色顏料的表面由染料分子所包覆。染料藉由吸附於顏料上而固著於顏料表面，因此染料的分子運動被抑制，藉此認為即便加熱，染料的分解亦被抑制，且認為使用本發明的著色感光性組成物而形成的著色層即便藉由加熱，亦抑制變色。另一方面，綠色顏料由於被染料包覆，故而即便綠色顏料藉由分散等而形成微粒子，所包覆的染料亦發揮作為保護膠體的作用，顏料的分散狀態得以穩定地保持，藉此推測綠色顏料的分散穩定性提高，對比度等提高。 In the present invention, a green pigment and a dye (having a mother skeleton different from the pigment) are used as a colorant to adsorb a part of the dye on the surface of the green pigment, whereby it is presumed that the surface of the green pigment is coated with the dye molecules. Since the dye is fixed to the surface of the pigment by being adsorbed on the pigment, the molecular motion of the dye is suppressed, and it is considered that the decomposition of the dye is suppressed even by heating, and the coloring formed by using the colored photosensitive composition of the present invention is considered to be colored. The layer suppresses discoloration even by heating. On the other hand, since the green pigment is coated with the dye, even if the green pigment forms fine particles by dispersion or the like, the coated dye functions as a protective colloid, and the dispersed state of the pigment is stably maintained, thereby presumably green. The dispersion stability of the pigment is improved, and the contrast and the like are improved.

於顏料分散液中混合染料(染料粉體或者溶解於有機溶劑中的染料溶液)的方法中，通常染料不吸附於顏料上或者即便吸附，吸附率亦小。相對於此，使用直接分散有綠色顏料及染料的分散組成物、或者預先製備包含綠色顏料及染料的有色材料混 合物，使用分散有該有色材料混合物的分散組成物來製備著色感光性組成物，從而獲得本發明的著色感光性組成物，該著色感光性組成物由於染料對顏料表面的吸附率增大，故而推測所得的著色層是耐熱性高，而且獲得高對比度的層。 In the method of mixing a dye (dye powder or a dye solution dissolved in an organic solvent) in a pigment dispersion, usually, the dye is not adsorbed on the pigment or the adsorption rate is small even if it is adsorbed. In contrast, a dispersion composition in which a green pigment and a dye are directly dispersed or a colored material containing a green pigment and a dye is prepared in advance. The coloring photosensitive composition of the present invention is obtained by using a dispersion composition in which the mixture of the colored materials is dispersed, thereby obtaining the coloring photosensitive composition of the present invention, which has an increased adsorption rate of the dye on the surface of the pigment. Therefore, it is presumed that the obtained coloring layer is high in heat resistance and a layer having high contrast is obtained.

依據本發明，可提供一種著色感光性組成物，該著色感光性組成物在形成彩色濾光片等的著色層的情況下，可形成耐熱性良好、亮度高、且對比度高的著色層。 According to the present invention, it is possible to provide a coloring photosensitive composition which can form a coloring layer which is excellent in heat resistance, high in brightness, and high in contrast when a coloring layer such as a color filter is formed.

另外，依據本發明，可提供使用上述著色感光性組成物而形成且可顯示亮度高、對比度高的影像的彩色濾光片及其製造方法，以及包括該彩色濾光片且可顯示良好畫質的顯示裝置。 Further, according to the present invention, it is possible to provide a color filter which is formed by using the above colored photosensitive composition and which can display an image having high luminance and high contrast, and a method of manufacturing the same, and a color filter which can display good image quality Display device.

1‧‧‧試驗片 1‧‧‧Test piece

2‧‧‧主電極 2‧‧‧Main electrode

3‧‧‧保護電極 3‧‧‧Protective electrode

4‧‧‧鉻表面 4‧‧‧Chromium surface

圖1是實施例的相對介電常數的測定中製作的主電極及保護電極的概略圖。 Fig. 1 is a schematic view showing a main electrode and a protective electrode produced in the measurement of the relative dielectric constant of the example.

本發明的著色感光性組成物的特徵在於：包含(A)綠色顏料、(B)具有與上述綠色顏料不同的母骨架的染料(以下適當稱為「特定染料」)、以及(C)聚合性化合物，並且特定染料的15質量%以上吸附於上述(A)綠色顏料的表面。 The colored photosensitive composition of the present invention is characterized by comprising (A) a green pigment, (B) a dye having a parent skeleton different from the above green pigment (hereinafter referred to as "specific dye" as appropriate), and (C) polymerizability The compound, and 15% by mass or more of the specific dye, is adsorbed on the surface of the above (A) green pigment.

此外，著色感光性組成物中的特定染料對綠色顏料表面的吸附率為特定染料的15質量%以上，較佳為20質量%以上。關 於吸附量的上限值，就本發明的主旨而言越高越佳，但若由染料過度包覆顏料表面，則存在阻礙分散劑的吸附的可能性，因此實際上為90質量%以下。 Further, the specific dye in the colored photosensitive composition has an adsorption rate on the surface of the green pigment of 15% by mass or more, preferably 20% by mass or more based on the specific dye. turn off The upper limit of the amount of adsorption is preferably as high as possible in the gist of the present invention. However, if the surface of the pigment is excessively coated with the dye, the adsorption of the dispersant may be inhibited. Therefore, it is actually 90% by mass or less.

另外，本說明書中，「~」表示其下限值以上且其上限值以下的範圍。另外，本說明書中的基團的表述中，未記載經取代及未經取代的表述不僅包含不具有取代基的基團，而且亦包含具有取代基的基團。 In the present specification, "~" indicates a range equal to or greater than the lower limit value and equal to or less than the upper limit value. Further, in the expression of the group in the present specification, the unsubstituted and unsubstituted expressions are not described as including not only a group having no substituent but also a group having a substituent.

進而，本說明書中，所謂「著色感光性組成物的總固體成分」，是指從構成著色感光性組成物的總成分中去除了有機溶劑的其餘成分的合計。 In the present specification, the "total solid content of the coloring photosensitive composition" means the total of the remaining components from which the organic solvent is removed from the total components constituting the colored photosensitive composition.

進而，本發明中，染料對顏料表面的吸附率定義為如下的染料吸附率，且以%表示，該染料吸附率是利用超離心分離機(日立工機(股)製造)以50000 rpm對分散組成物進行離心處理，採集包含游離成分的上清液，利用高效液相層析法(high performance liquid chromatography，HPLC)來測定所得上清液中的染料量，且根據以下數學式而獲得。 Further, in the present invention, the adsorption rate of the dye on the surface of the pigment is defined as the dye adsorption rate, which is expressed in %, and the dye adsorption rate is dispersed by using an ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) at 50,000 rpm. The composition was subjected to centrifugation, and the supernatant containing the free component was collected, and the amount of the dye in the obtained supernatant was measured by high performance liquid chromatography (HPLC), and was obtained according to the following mathematical formula.

〈著色感光性組成物〉 <Coloring photosensitive composition>

以下，對構成本發明著色感光性組成物的必需成分及任意成分進行說明。 Hereinafter, the essential components and optional components constituting the colored photosensitive composition of the present invention will be described.

本發明的著色感光性組成物是以(A)綠色顏料、(B)特定染料、以及(C)聚合性化合物作為必需成分。 The colored photosensitive composition of the present invention contains (A) a green pigment, (B) a specific dye, and (C) a polymerizable compound as essential components.

[(A)綠色顏料] [(A) Green Pigment]

本發明的著色感光性組成物中包含(A)綠色顏料，該綠色顏料可使用綠色有機顏料、綠色無機顏料中的任一種，較佳為綠色有機顏料。 The coloring photosensitive composition of the present invention contains (A) a green pigment, and any of a green organic pigment and a green inorganic pigment can be used as the green pigment, and a green organic pigment is preferable.

綠色有機顏料例如較佳為C.I.顏料綠(Pigment Green)7、10、36、37及58，該些顏料中較佳為C.I.顏料綠7、36、37及58。 The green organic pigment is, for example, preferably C.I. Pigment Green 7, 10, 36, 37 and 58, and among these pigments, C.I. Pigment Green 7, 36, 37 and 58 are preferred.

另外，關於綠色顏料的平均一次粒徑，若考慮到較佳為高穿透率，則較佳為儘可能選擇粒徑小且微小的粒子尺寸(grain size)的顏料。尤其若亦考慮到操作性，則綠色顏料較佳為平均一次粒徑為0.01 μm~0.3 μm、更佳為0.01 μm~0.15 μm的顏料。若粒徑為上述範圍內，則對於形成穿透率高、色特性良好、並且高對比度的彩色濾光片而言有效。 Further, as for the average primary particle diameter of the green pigment, in consideration of the fact that the high specific transmittance is preferable, it is preferred to select a pigment having a small particle size and a small grain size as much as possible. In particular, if operability is also considered, the green pigment is preferably a pigment having an average primary particle diameter of 0.01 μm to 0.3 μm, more preferably 0.01 μm to 0.15 μm. When the particle diameter is within the above range, it is effective for forming a color filter having high transmittance, good color characteristics, and high contrast.

平均一次粒徑是藉由利用掃描式電子顯微鏡(scanning electron microscope，SEM)或者穿透式電子顯微鏡(transmission electron microscope，TEM)來觀察粒子，在粒子未凝聚的部分計測100個粒子尺寸，算出平均值而求出。 The average primary particle diameter is observed by a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured in a portion where the particles are not aggregated, and an average is calculated. Find the value.

本發明的著色感光性組成物中，視需要為了調色等，亦可併用綠色顏料以外的有機顏料、無機顏料。 In the colored photosensitive composition of the present invention, an organic pigment or an inorganic pigment other than the green pigment may be used in combination for coloring or the like as needed.

可併用的綠色顏料以外的顏料例如可列舉下述有機顏料。但，本發明中，可併用的顏料並不限定於該些顏料。 Examples of the pigment other than the green pigment which can be used in combination include the following organic pigments. However, in the present invention, the pigments which can be used in combination are not limited to the pigments.

C.I.顏料紅1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48：1、48：2、48：3、48：4、49、49：1、49：2、52：1、52：2、53：1、57：1、60：1、63：1、66、67、81：1、81：2、81：3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、270、272、279；C.I.顏料黃1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35：1、36、36：1、37、37：1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214； C.I.顏料橙2、5、13、16、17：1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73；C.I.顏料藍1、2、15、15：1、15：2、15：3、15：4、15：6、16、22、60、64、66、79、將79的Cl取代基變更為OH的顏料、80；C.I.顏料紫1、19、23、27、32、37、42；C.I.顏料棕25、28；C.I.顏料黑1。 CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279; CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167 168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214; CI Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 CI pigment blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, changing the Cl substituent of 79 to OH pigment, 80; CI pigment violet 1, 19, 23, 27, 32, 37, 42; CI pigment brown 25, 28; CI pigment black 1.

該些顏料中可較佳使用的有機顏料可列舉以下顏料。 Among the pigments which can be preferably used, the following pigments can be exemplified.

C.I.顏料黃11、24、108、109、110、138、139、150、151、154、167、180、185；C.I.顏料橙36、71；C.I.顏料紅122、150、171、175、177、209、224、242、254、255、264；C.I.顏料藍15：1、15：3、15：6、16、22、60、66；C.I.顏料紫19、23、32；C.I.顏料黑1。 CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185; CI Pigment Orange 36, 71; CI Pigment Red 122, 150, 171, 175, 177, 209 224, 242, 254, 255, 264; CI Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66; CI Pigment Violet 19, 23, 32; CI Pigment Black 1.

另外，無機顏料可列舉金屬氧化物、金屬錯鹽等所表示的金屬化合物，具體而言可列舉：鐵、鈷、鋁、鎘、鉛、銅、鈦、鎂、鉻、鋅、銻等的金屬氧化物，以及上述金屬的複合氧化物。 In addition, examples of the inorganic pigment include a metal compound represented by a metal oxide or a metal salt, and specific examples thereof include metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. An oxide, and a composite oxide of the above metals.

[(B)特定染料] [(B) specific dye]

本發明的著色感光性組成物包含具有與(A)綠色顏料不同的母骨架的染料(=特定染料)。 The colored photosensitive composition of the present invention contains a dye (=specific dye) having a parent skeleton different from the (A) green pigment.

所謂母骨架，是指具有染料的結構及色相的特徵的結構部，例如可列舉酞花青、吡咯亞甲基(pyrromethene)、蒽醌(anthraquinone)等結構。 The parent skeleton refers to a structure having a structure of a dye and a characteristic of a hue, and examples thereof include a structure such as phthalocyanine, pyrromethene, and anthraquinone.

特定染料只要是具有與上述綠色顏料不同的母骨架的染料，則並無特別限制，就化學結構而言，可使用：吡咯亞甲基系、吡唑偶氮(pyrazole azo)系、苯胺基偶氮(anilino azo)系、三苯基甲烷(triphenylmethane)系、蒽醌系、蒽吡啶酮(anthrapyridone)系、苯亞甲基(benzylidene)系、氧喏(oxonol)系、吡唑并***偶氮(pyrazolotriazole azo)系、吡啶酮偶氮(pyridone azo)系、花青(cyanine)系、吩噻嗪(phenothiazine)系、吡咯并吡唑偶氮次甲基(pyrrolopyrazole azomethine)系、氧雜蒽(xanthene)系、酞花青系、苯并哌喃(benzopyran)系、靛藍(indigo)系等的染料。 The specific dye is not particularly limited as long as it is a dye having a parent skeleton different from the above-described green pigment. In terms of chemical structure, pyrrolemethylene, pyrazole azo, or anilino can be used. Nilino azo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole Nitrogen (pyrazolotriazole azo), pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene A dye such as (xanthene), phthalocyanine, benzopyran or indigo.

該些具體例例如可列舉以下專利文獻中記載的色素：日本專利特開昭64-90403號公報、日本專利特開昭64-91102號公報、日本專利特開平1-94301號公報、日本專利特開平6-11614號公報、日本專利特登2592207號、美國專利第4,808,501號說明書、美國專利第5,667,920號說明書、美國專利第5,059,500號說明書、日本專利特開平5-333207號公報、日本專利特開平6-35183號公 報、日本專利特開平6-51115號公報、日本專利特開平6-194828號公報、日本專利特開平8-211599號公報、日本專利特開平4-249549號公報、日本專利特開平10-123316號公報、日本專利特開平11-302283號公報、日本專利特開平7-286107號公報、日本專利特開2001-4823號公報、日本專利特開平8-15522號公報、日本專利特開平8-29771號公報、日本專利特開平8-146215號公報、日本專利特開平11-343437號公報、日本專利特開平8-62416號公報、日本專利特開2002-14220號公報、日本專利特開2002-14221號公報、日本專利特開2002-14222號公報、日本專利特開2002-14223號公報、日本專利特開平8-302224號公報、日本專利特開平8-73758號公報、日本專利特開平8-179120號公報、日本專利特開平8-151531號公報等。 For example, the pigments described in the following patent documents are disclosed in Japanese Patent Laid-Open Publication No. SHO-64-90403, Japanese Patent Application Laid-Open No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -35183 Japanese Patent Laid-Open No. Hei 6-51115, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8-146215, Japanese Patent Laid-Open No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2002-14222, Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 8-151531, and the like.

另外，特定染料的顏色較佳為呈現出黃色。 In addition, the color of the particular dye preferably exhibits a yellow color.

(較佳的特定染料) (better specific dye)

該些特定染料中，吡唑并***次甲基染料在分子內包含1個或者多個吡唑并***環，較佳為夾持次甲基鏈而包含各為1個、共計2個的吡唑并***環。另外，具有由奇數個次甲基形成的次甲基鏈的情況亦為較佳實施方式。就作為本發明目的的色再現的觀點而言，次甲基的數量較佳為1個。具體而言為下述通式(a-1)以及通式(a-2)所表示的化合物。 Among the specific dyes, the pyrazolotriazole methine dye contains one or more pyrazolotriazole rings in the molecule, preferably one of the methine chains and one each, for a total of two Pyrazole triazole ring. Further, the case of having a methine chain formed of an odd number of methine groups is also a preferred embodiment. From the viewpoint of color reproduction which is the object of the present invention, the number of methine groups is preferably one. Specifically, it is a compound represented by the following general formula (a-1) and general formula (a-2).

就色再現及亮度的觀點而言，適合於本發明著色感光性 組成物的特定染料較佳為選自由下述通式(a-1)、通式(a-2)、通式(b)以及通式(c)所表示的化合物所組成組群中的至少一個。 Suitable for coloring photosensitivity of the present invention from the viewpoint of color reproduction and brightness The specific dye of the composition is preferably at least selected from the group consisting of compounds represented by the following general formula (a-1), general formula (a-2), general formula (b), and general formula (c). One.

以下對通式(a-1)、通式(a-2)、通式(b)以及通式(c)所表示的化合物進行詳細說明。 Hereinafter, the compounds represented by the general formula (a-1), the general formula (a-2), the general formula (b), and the general formula (c) will be described in detail.

通式(a-1)及通式(a-2)中，R1~R5分別獨立地表示氫原子、或者一價取代基。 In the general formula (a-1) and the general formula (a-2), R 1 to R 5 each independently represent a hydrogen atom or a monovalent substituent.

R1~R5所表示的一價取代基具體而言可列舉：烷基、芳基、全氟烷基羰基、烷基磺醯基、烯基磺醯基、芳基磺醯基、雜環磺醯基、胺磺醯基、烷基胺磺醯基、芳基胺磺醯基、或者雜環胺磺醯基等。 Specific examples of the monovalent substituent represented by R 1 to R 5 include an alkyl group, an aryl group, a perfluoroalkylcarbonyl group, an alkylsulfonyl group, an alkenylsulfonyl group, an arylsulfonyl group, and a heterocyclic ring. A sulfonyl group, an amine sulfonyl group, an alkylamine sulfonyl group, an arylamine sulfonyl group, or a heterocyclic amine sulfonyl group.

該些各基團可進一步具有取代基，R1~R5所表示的各一價取代基的總碳數為1~40的範圍，較佳為3~25的範圍。藉由設為該範圍，則著色感光性組成物的保存穩定性良好，且獲得亮度高的著色感光性組成物。 Each of these groups may further have a substituent, and the total carbon number of each monovalent substituent represented by R 1 to R 5 is in the range of 1 to 40, preferably in the range of 3 to 25. When it is set to this range, the storage stability of the coloring photosensitive composition is good, and the coloring photosensitive composition with high brightness is obtained.

尤其，通式(a-1)及通式(a-2)所表示的化合物較佳 為以下的實施方式。 In particular, the compound represented by the formula (a-1) and the formula (a-2) is preferably a compound It is the following embodiment.

即，R1、R2為直鏈或者分支的烷基，R4、R5為烷基或者芳基，且R3為氫原子、烷基、或者芳基的實施方式。 That is, R 1 and R 2 are a linear or branched alkyl group, and R 4 and R 5 are an alkyl group or an aryl group, and R 3 is a hydrogen atom, an alkyl group or an aryl group.

以下，表示本發明的通式(a-1)及通式(a-2)所表示的吡唑并***次甲基染料的具體例，但本發明並不限定於該些具體例。 Specific examples of the pyrazolotriazole methine dye represented by the general formula (a-1) and the general formula (a-2) of the present invention are shown below, but the present invention is not limited to these specific examples.

通式(b)中，R6及R7分別獨立地表示氫原子、或者一價取代基。R8表示氫原子、脂肪族基、芳基、雜環基、胺甲醯基、烷氧基羰基、芳氧基羰基、醯基、烷基磺醯基、芳基磺醯基、或者胺磺醯基。Q表示重氮成分殘基。通式(b)所表示的色素可在任意位置形成二聚物以上的多聚物。 In the formula (b), R 6 and R 7 each independently represent a hydrogen atom or a monovalent substituent. R 8 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an amine carbenyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonate.醯基. Q represents a diazo component residue. The dye represented by the formula (b) can form a polymer of a dimer or more at any position.

具體而言，R6及R7所表示的一價取代基分別獨立地表示：鹵素原子、脂肪族基、芳基、雜環基、氰基、羧基、胺甲醯基、脂肪族氧羰基、芳氧基羰基、醯基、羥基、脂肪族氧基、芳氧基、醯氧基、胺甲醯氧基、雜環氧基、胺基、脂肪族胺基、芳基胺基、雜環胺基、醯基胺基、胺甲醯基胺基、胺磺醯基胺基、脂肪族氧羰基胺基、芳氧基羰基胺基、脂肪族磺醯基胺基、芳基磺醯基胺基、硝基、脂肪族硫基、芳硫基、脂肪族磺醯基、芳基磺醯基、胺磺醯基、磺基、醯亞胺基、或者雜環硫基。該些基團中，主要就賦予溶解性的觀點而言，較佳為脂肪族基、芳基、雜環基、氰基、胺甲醯基、脂肪族氧羰基、芳氧基羰基、醯基、脂肪族氧基、芳氧基、脂肪族胺基、或者芳基胺基。 Specifically, the monovalent substituents represented by R 6 and R 7 each independently represent a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an amine formazan group, an aliphatic oxycarbonyl group, Aryloxycarbonyl, fluorenyl, hydroxy, aliphatic oxy, aryloxy, decyloxy, amine methyl methoxy, heterocyclic oxy, amine, aliphatic amine, aryl amine, heterocyclic amine Base, mercaptoamine, amine mercaptoamine, amine sulfonylamino, aliphatic oxycarbonylamino, aryloxycarbonylamino, aliphatic sulfonylamino, arylsulfonylamino A nitro group, an aliphatic thio group, an arylthio group, an aliphatic sulfonyl group, an arylsulfonyl group, an amine sulfonyl group, a sulfo group, a quinone imine group, or a heterocyclic thio group. Among these groups, from the viewpoint of imparting solubility, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, an aminomethyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, or a fluorenyl group are preferred. An aliphatic oxy group, an aryloxy group, an aliphatic amine group, or an arylamine group.

該些各基團可進一步經取代，而且R1~R5所表示的各一價取代基的總碳數為1~40的範圍，較佳為3~25的範圍。藉由設為該範圍，則著色感光性組成物的保存穩定性良好，且獲得亮度高的著色感光性組成物。 Each of the groups may be further substituted, and the total carbon number of each monovalent substituent represented by R 1 to R 5 is in the range of 1 to 40, preferably in the range of 3 to 25. When it is set to this range, the storage stability of the coloring photosensitive composition is good, and the coloring photosensitive composition with high brightness is obtained.

R6~R8所表示的脂肪族基可具有取代基，可為飽和，亦 可為不飽和，亦可為環狀。具體而言，例如可列舉：烷基、經取代的烷基、烯基、經取代的烯基、炔基、經取代的炔基、芳烷基及經取代的芳烷基等。脂肪族基的總碳數較佳為1~30，尤佳為1~16。脂肪族基的具體例例如可列舉：甲基、乙基、丁基、異丙基、第三丁基、羥基乙基、甲氧基乙基、氰基乙基、三氟甲基、3-磺基丙基、4-磺基丁基、環己基、苄基、2-苯乙基、乙烯基、及烯丙基等。 The aliphatic group represented by R 6 to R 8 may have a substituent, may be saturated, may be unsaturated, or may be cyclic. Specific examples thereof include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The total carbon number of the aliphatic group is preferably from 1 to 30, particularly preferably from 1 to 16. Specific examples of the aliphatic group include methyl group, ethyl group, butyl group, isopropyl group, tert-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, and 3- Sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenylethyl, vinyl, and allyl groups, and the like.

R6~R8所表示的芳基可具有取代基，較佳為總碳數為6~30的芳基，尤佳為總碳數6~16的芳基。具體而言，例如可列舉：苯基、4-甲苯基、4-甲氧基苯基、2-氯苯基、3-(3-磺基丙基胺基)苯基、4-胺磺醯基、4-乙氧基乙胺磺醯基及3-二甲基胺甲醯基等。 The aryl group represented by R 6 to R 8 may have a substituent, preferably an aryl group having a total carbon number of 6 to 30, and particularly preferably an aryl group having a total carbon number of 6 to 16. Specific examples thereof include a phenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, a 2-chlorophenyl group, a 3-(3-sulfopropylamino)phenyl group, and a 4-amine sulfonium oxime. Base, 4-ethoxyethylamine sulfonyl group and 3-dimethylaminecarbamyl group.

R6~R8所表示的雜環基可為飽和，亦可為不飽和，包含以下的芳香族雜環基，可列舉環內包含氮原子、硫原子、氧原子等雜原子的任一者的雜環基，可進一步具有取代基，較佳為總碳數1~30的雜環基，尤佳為總碳數1~15的雜環基。具體而言，例如可列舉：2-吡啶基、2-噻吩基、2-噻唑基、2-苯并噻唑基、2-苯并噁唑基及2-呋喃基等。 The heterocyclic group represented by R 6 to R 8 may be saturated or unsaturated, and may include the following aromatic heterocyclic group, and may include any of a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom in the ring. The heterocyclic group may further have a substituent, preferably a heterocyclic group having a total carbon number of 1 to 30, and particularly preferably a heterocyclic group having a total carbon number of 1 to 15. Specific examples thereof include a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a 2-benzoxazolyl group, and a 2-furyl group.

R6~R8所表示的胺甲醯基可具有取代基，較佳為總碳數1~30的胺甲醯基，尤佳為碳原子數1~16的胺甲醯基。具體而言，例如可列舉：甲基胺甲醯基、二甲基胺甲醯基、苯基胺甲醯 基及N-甲基-N-苯基胺甲醯基等。 The amine carbenyl group represented by R 6 to R 8 may have a substituent, preferably an amine carbenyl group having a total carbon number of 1 to 30, and particularly preferably an amine carbenyl group having 1 to 16 carbon atoms. Specific examples thereof include a methylamine methyl sulfonyl group, a dimethylamine methyl fluorenyl group, a phenylamine methyl sulfonyl group, and an N-methyl-N-phenylamine methyl fluorenyl group.

R6~R8所表示的脂肪族氧羰基可具有取代基，可為飽和，亦可為不飽和，亦可為環狀，較佳為總碳數2~30的脂肪族氧羰基，尤佳為總碳數2~16的脂肪族氧羰基。具體而言，例如可列舉：甲氧基羰基、乙氧基羰基及2-甲氧基乙氧基羰基等。 The aliphatic oxycarbonyl group represented by R 6 to R 8 may have a substituent, may be saturated, may be unsaturated, or may be cyclic, preferably an aliphatic oxycarbonyl group having a total carbon number of 2 to 30, particularly preferably It is an aliphatic oxycarbonyl group having a total carbon number of 2 to 16. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a 2-methoxyethoxycarbonyl group.

R6~R8所表示的芳氧基羰基可具有取代基，較佳為總碳數7~30的芳氧基羰基，尤佳為碳原子數7~16的芳氧基羰基。具體而言，例如可列舉：苯氧基羰基、4-甲基苯氧基羰基及3-氯苯氧基羰基等。 The aryloxycarbonyl group represented by R 6 to R 8 may have a substituent, preferably an aryloxycarbonyl group having a total carbon number of 7 to 30, and particularly preferably an aryloxycarbonyl group having 7 to 16 carbon atoms. Specific examples thereof include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, and a 3-chlorophenoxycarbonyl group.

R6~R8所表示的醯基中包含脂肪族羰基、芳基羰基、及雜環羰基，較佳為總碳數為1~30的實施方式，尤佳為總碳數為1~16的實施方式。具體而言，例如可列舉：乙醯基、甲氧基乙醯基、噻吩甲醯基(thenoyl)及苯甲醯基等。 The mercapto group represented by R 6 to R 8 includes an aliphatic carbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, preferably an embodiment having a total carbon number of 1 to 30, and particularly preferably a total carbon number of 1 to 16. Implementation. Specific examples thereof include an ethyl fluorenyl group, a methoxyethyl fluorenyl group, a thiophenemethyl group (thenoyl group), and a benzamidine group.

R6~R8所表示的脂肪族磺醯基可具有取代基，可為飽和，亦可為不飽和，亦可為環狀，較佳為總碳數1~30的實施方式，尤佳為總碳數1~16的實施方式。具體而言，例如可列舉：甲磺醯基、甲氧基甲磺醯基及乙氧基乙磺醯基等。 The aliphatic sulfonyl group represented by R 6 to R 8 may have a substituent, may be saturated, may be unsaturated, or may be cyclic, preferably an embodiment having a total carbon number of 1 to 30, particularly preferably An embodiment with a total carbon number of 1 to 16. Specific examples thereof include a methanesulfonyl group, a methoxymethanesulfonyl group, and an ethoxyethanesulfonyl group.

R6~R8所表示的芳基磺醯基可具有取代基，較佳為總碳數6~30的實施方式，尤佳為總碳數6~18的實施方式。具體而言，例如可列舉：苯磺醯基及甲苯磺醯基等。 The arylsulfonyl group represented by R 6 to R 8 may have a substituent, preferably an embodiment having a total carbon number of 6 to 30, and particularly preferably an embodiment having a total carbon number of 6 to 18. Specific examples thereof include a benzenesulfonyl group and a toluenesulfonyl group.

R6~R8所表示的胺磺醯基可具有取代基，較佳為總碳數 0~30的實施方式，尤佳為總碳數0~16的實施方式。具體而言，例如可列舉：胺磺醯基、二甲基胺磺醯基及二-(2-羥基乙基)胺磺醯基等。 The amine sulfonyl group represented by R 6 to R 8 may have a substituent, preferably an embodiment having a total carbon number of 0 to 30, and particularly preferably an embodiment having a total carbon number of 0 to 16. Specific examples thereof include an aminesulfonyl group, a dimethylaminesulfonyl group, and a di-(2-hydroxyethyl)aminesulfonyl group.

R6~R8所表示的醯亞胺基可具有取代基，較佳為5員~6員環的醯亞胺基。另外，醯亞胺基的總碳數較佳為4~30的實施方式，尤佳為4~20的實施方式。具體而言，例如可列舉：丁二醯亞胺及鄰苯二甲醯亞胺基等。 The quinone imine group represented by R 6 to R 8 may have a substituent, and is preferably a quinone imine group of 5 to 6 membered rings. Further, the total carbon number of the quinone imine group is preferably from 4 to 30, and particularly preferably from 4 to 20. Specific examples include, for example, succinimide and phthalimido group.

Q所表示的重氮成分殘基是指重氮成分「B-NH2」的殘基。尤其就作為目標的色再現性的方面而言，Q較佳為芳基或者芳香族雜環基。 The residue of the diazo component represented by Q means a residue of the diazo component "B-NH 2 ". In particular, in terms of the intended color reproducibility, Q is preferably an aryl group or an aromatic heterocyclic group.

此處，所謂芳香族雜環基，是指環內包含氮原子、硫原子、氧原子等雜原子的任一者的芳香族環，較佳為5員~6員環。芳香族雜環基的碳原子數較佳為1~25，尤佳為1~15。芳香族雜環具體而言可列舉：吡唑基、1,2,4-***基、異噻唑基、苯并異噻唑基、噻唑基、苯并噻唑基、噁唑基、1,2,4-噻二唑基等。 Here, the aromatic heterocyclic group refers to an aromatic ring containing any one of a hetero atom such as a nitrogen atom, a sulfur atom or an oxygen atom, and preferably has a 5-member to 6-membered ring. The aromatic heterocyclic group preferably has 1 to 25 carbon atoms, and more preferably 1 to 15 carbon atoms. Specific examples of the aromatic heterocyclic ring include pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazolyl, thiazolyl, benzothiazolyl, oxazolyl, 1,2, 4-thiadiazolyl and the like.

尤其，通式(b)所表示的化合物較佳為以下實施方式。 In particular, the compound represented by the formula (b) is preferably the following embodiment.

即，R6為氰基、脂肪族氧羰基或者胺甲醯基，R7為脂肪族基，R8為脂肪族基、醯基、芳基、脂肪族羰基、脂肪族磺醯基或者芳基磺醯基，且Q為芳基的實施方式。 That is, R 6 is a cyano group, an aliphatic oxycarbonyl group or an amine carbaryl group, R 7 is an aliphatic group, and R 8 is an aliphatic group, a fluorenyl group, an aryl group, an aliphatic carbonyl group, an aliphatic sulfonyl group or an aryl group. An embodiment of a sulfonyl group and Q is an aryl group.

以下，表示本發明的通式(b)所表示的吡啶酮偶氮染料的具體例，但本發明並不限定於該些具體例。 Specific examples of the pyridone azo dye represented by the formula (b) of the present invention are shown below, but the present invention is not limited to these specific examples.

通式(c)中，R9及R10分別獨立地表示氫原子、或者一價取代基。R11表示氫原子、脂肪族基、芳基、雜環基、胺甲醯基、烷氧基羰基、芳氧基羰基、醯基、烷基磺醯基、芳基磺醯基、或者胺磺醯基，A表示重氮成分殘基。 In the formula (c), R 9 and R 10 each independently represent a hydrogen atom or a monovalent substituent. R 11 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an amine mercapto group, an alkoxycarbonyl group, an aryloxycarbonyl group, a decyl group, an alkylsulfonyl group, an arylsulfonyl group, or an amine sulfonate. Amidino, A represents a diazo component residue.

具體而言，R9及R10所表示的一價取代基分別獨立地表示：鹵素原子、脂肪族基、芳基、雜環基、氰基、羧基、胺甲醯基、脂肪族氧羰基、芳氧基羰基、醯基、羥基、脂肪族氧基、芳氧基、醯氧基、胺甲醯氧基、雜環氧基、胺基、脂肪族胺基、芳基胺基、雜環胺基、醯基胺基、胺甲醯基胺基、胺磺醯基胺基、脂肪族氧羰基胺基、芳氧基羰基胺基、脂肪族磺醯基胺基、芳基 磺醯基胺基、硝基、脂肪族硫基、芳硫基、脂肪族磺醯基、芳基磺醯基、胺磺醯基、磺基、醯亞胺基、或者雜環硫基，主要就賦予溶解性的觀點而言，較佳為脂肪族基、芳基、雜環基、氰基、胺甲醯基、脂肪族氧羰基、芳氧基羰基、醯基、脂肪族氧基、芳氧基、脂肪族胺基、芳基胺基。 Specifically, the monovalent substituents represented by R 9 and R 10 each independently represent a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a carboxyl group, an amine formazan group, an aliphatic oxycarbonyl group, Aryloxycarbonyl, fluorenyl, hydroxy, aliphatic oxy, aryloxy, decyloxy, amine methyl methoxy, heterocyclic oxy, amine, aliphatic amine, aryl amine, heterocyclic amine Base, mercaptoamine, amine mercaptoamine, amine sulfonylamino, aliphatic oxycarbonylamino, aryloxycarbonylamino, aliphatic sulfonylamino, arylsulfonylamino , nitro, aliphatic thio, arylthio, aliphatic sulfonyl, arylsulfonyl, sulfonyl, sulfo, sulfhydrido, or heterocyclic thio, mainly imparting solubility From the viewpoint, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, an aminomethyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a decyl group, an aliphatic oxy group, an aryloxy group, or an aliphatic group are preferred. Amine, arylamine group.

該些各基團可進一步經取代，R1~R5所表示的各一價取代基的總碳數為1~40的範圍，較佳為3~25的範圍。藉由設為該範圍，則著色感光性組成物的保存穩定性良好，且獲得亮度高的著色感光性組成物。 Each of the groups may be further substituted, and the total carbon number of each monovalent substituent represented by R 1 to R 5 is in the range of 1 to 40, preferably in the range of 3 to 25. When it is set to this range, the storage stability of the coloring photosensitive composition is good, and the coloring photosensitive composition with high brightness is obtained.

R9~R11所表示的脂肪族基可具有取代基，可為飽和，亦可為不飽和，亦可為環狀。具體而言，例如可列舉：烷基、經取代的烷基、烯基、經取代的烯基、炔基、經取代的炔基、芳烷基及經取代的芳烷基等。脂肪族基的總碳數較佳為1~30，尤佳為1~16。脂肪族基的具體例例如可列舉：甲基、乙基、丁基、異丙基、第三丁基、羥基乙基、甲氧基乙基、氰基乙基、三氟甲基、3-磺基丙基、4-磺基丁基、環己基、苄基、2-苯乙基、乙烯基、及烯丙基等。 The aliphatic group represented by R 9 to R 11 may have a substituent, may be saturated, may be unsaturated, or may be cyclic. Specific examples thereof include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group, and a substituted aralkyl group. The total carbon number of the aliphatic group is preferably from 1 to 30, particularly preferably from 1 to 16. Specific examples of the aliphatic group include methyl group, ethyl group, butyl group, isopropyl group, tert-butyl group, hydroxyethyl group, methoxyethyl group, cyanoethyl group, trifluoromethyl group, and 3- Sulfopropyl, 4-sulfobutyl, cyclohexyl, benzyl, 2-phenylethyl, vinyl, and allyl groups, and the like.

A所表示的重氮成分殘基是指重氮成分「B-NH2」的殘基。尤其就作為目標的色再現性的方面而言，A較佳為芳基或者芳香族雜環基。 The diazo component residue represented by A is a residue of the diazo component "B-NH 2 ". In particular, in terms of the target color reproducibility, A is preferably an aryl group or an aromatic heterocyclic group.

此處，所謂芳香族雜環基，是指環內包含氮原子、硫原 子、氧原子等雜原子的任一者的芳香族環，較佳為5員~6員環。芳香族雜環基的碳原子數較佳為1~25，尤佳為1~15。芳香族雜環具體而言可列舉：吡唑基、1,2,4-***基、異噻唑基、苯并異噻唑基、噻唑基、苯并噻唑基、噁唑基、1,2,4-噻二唑基等。 Here, the term "aromatic heterocyclic group" means that a nitrogen atom or a sulfur atom is contained in the ring. The aromatic ring of any of the hetero atoms such as a child and an oxygen atom is preferably a 5- to 6-membered ring. The aromatic heterocyclic group preferably has 1 to 25 carbon atoms, and more preferably 1 to 15 carbon atoms. Specific examples of the aromatic heterocyclic ring include pyrazolyl, 1,2,4-triazolyl, isothiazolyl, benzisothiazolyl, thiazolyl, benzothiazolyl, oxazolyl, 1,2, 4-thiadiazolyl and the like.

以下，表示本發明的通式(c)所表示的染料的具體例，但本發明並不限定於該些具體例。 Specific examples of the dye represented by the general formula (c) of the present invention are shown below, but the present invention is not limited to these specific examples.

[分散組成物] [dispersed composition]

本發明的著色感光性組成物較佳為包含分散組成物。作為獲得本發明著色感光性組成物的方法，對較佳包含的分散組成 物進行說明。 The colored photosensitive composition of the present invention preferably contains a dispersion composition. As a method of obtaining the coloring photosensitive composition of the present invention, a dispersion composition preferably included The object is explained.

本發明的著色感光性組成物中，(B)特定染料的15質量%以上吸附於(A)綠色顏料的表面。藉由將(B)特定染料對(A)綠色顏料表面的吸附率設為上述範圍，則利用本發明的著色感光性組成物而獲得的著色層的耐熱性良好，可顯示高對比度。使特定染料吸附於綠色顏料上的方法可為任一種方法，但較佳為預先製備包含綠色顏料及特定染料的分散組成物。 In the colored photosensitive composition of the present invention, (B) 15% by mass or more of the specific dye is adsorbed on the surface of the (A) green pigment. When the adsorption ratio of the (B) specific dye to the surface of the (A) green pigment is in the above range, the coloring layer obtained by using the colored photosensitive composition of the present invention has good heat resistance and can exhibit high contrast. The method of adsorbing a specific dye on the green pigment may be either a method, but it is preferred to prepare a dispersion composition containing a green pigment and a specific dye in advance.

(有色材料組成物) (colored material composition)

另外，為了獲得該分散組成物，較佳為將綠色顏料與特定染料預混合而製成有色材料組成物，然後在同一系統內進行分散處理而製成分散組成物。即，較佳為預先製備將顏料與染料，視需要將溶劑或分散劑、添加劑、研磨劑等進行混合而成的漿料(有色材料組成物)，將該漿料總括地投入於分散系統中進行分散處理。因此，本發明中在進行後述的鹽研磨之前、或者以分散機進行分散處理之前，進一步利用分散機進行多階段分散處理的情況下，將在該各階段之前，任一者均將預先混合有染料的漿料進行分散處理的情況下稱為預混合。此外，上述所謂「同一系統內」，是指在同一分散裝置內，且在同一分散批次內進行分散處理。 Further, in order to obtain the dispersion composition, it is preferred to preliminarily mix a green pigment with a specific dye to prepare a colored material composition, and then perform dispersion treatment in the same system to prepare a dispersion composition. In other words, it is preferred to prepare a slurry (colored material composition) obtained by mixing a pigment and a dye, if necessary, a solvent or a dispersant, an additive, an abrasive, or the like, and the slurry is collectively introduced into a dispersion system. Disperse treatment. Therefore, in the present invention, in the case where the multi-stage dispersion treatment is further carried out by a disperser before the salt polishing described later or before the dispersion treatment by the disperser, any of the stages may be pre-mixed before In the case where the slurry of the dye is subjected to dispersion treatment, it is referred to as pre-mixing. In addition, the above-mentioned "in the same system" means that the dispersion treatment is performed in the same dispersion batch in the same dispersion apparatus.

預混合的方法可選擇多種方法，可使用後述(F)有機溶劑將綠色顏料與固體的特定染料進行混合，或者亦可將綠色顏料、與在後述(F)有機溶劑中溶解有特定染料的染料溶液進行混 合。 The premixing method may be selected from a plurality of methods, and the green pigment may be mixed with a solid specific dye using the organic solvent (F) described later, or the green pigment may be mixed with a dye having a specific dye dissolved in the organic solvent (F) described later. Solution mixing Hehe.

混合的方法可為通常的使用攪拌機等的方法，亦可為使用二輥機、三輥機、球磨機、轉筒篩磨機(trommel mill)、分散機、捏合機、雙向捏合機(ko-kneader)、均質機、摻合機、單軸或雙軸的擠出機等，一邊賦予強的剪切力一邊進行混練的方法，就增大染料的吸附率的觀點而言，較佳為進行混練的方法。 The mixing method may be a usual method using a stirrer or the like, or a two-roll mill, a three-roll mill, a ball mill, a trummel mill, a disperser, a kneader, a two-way kneader (ko-kneader) ), a homogenizer, a blender, a uniaxial or biaxial extruder, etc., and a method of kneading while imparting a strong shearing force, and it is preferable to carry out kneading from the viewpoint of increasing the adsorption rate of the dye. Methods.

(鹽研磨) (salt grinding)

顏料通常會凝聚，為了在分散前預先進行碎裂，較佳為進行後述的鹽研磨處理作為顏料微細化處理。此時，作為染料與顏料的混合方法，可在鹽研磨處理時以溶液狀或者固體狀添加特定染料來製備上述有色材料組成物。 The pigment usually aggregates, and in order to preliminarily break before dispersion, it is preferred to carry out a salt polishing treatment to be described later as a pigment refining treatment. At this time, as a method of mixing the dye and the pigment, the above colored material composition can be prepared by adding a specific dye in the form of a solution or a solid during the salt polishing treatment.

顏料的微細化是藉由經過如下步驟(鹽研磨)來達成：與顏料、水溶性有機溶劑及水溶性無機鹽類一起製備高黏度的液狀組成物，使用濕式粉碎裝置等，施加應力來磨碎。此時，視需要，可將特定染料以溶液狀或者固體狀而與顏料一起添加，來獲得有色材料混合物。 The refinement of the pigment is achieved by the following steps (salt grinding): preparing a high-viscosity liquid composition together with a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt, and applying a stress using a wet pulverizing device or the like grinding. At this time, a specific dye may be added together with the pigment in a solution or a solid as needed to obtain a colored material mixture.

顏料的微細化步驟中使用的水溶性有機溶劑可列舉：甲醇、乙醇、異丙醇、正丙醇、異丁醇、正丁醇、乙二醇、二乙二醇、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇、丙二醇單甲醚乙酸酯等。 The water-soluble organic solvent used in the micronization step of the pigment may, for example, be methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol, ethylene glycol, diethylene glycol or diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, and the like.

另外，亦可使用水溶性低，或者不具有水溶性的其他溶 劑，例如：苯、甲苯、二甲苯、乙基苯、氯苯、硝基苯、苯胺、吡啶、喹啉、四氫呋喃、二噁烷、乙酸乙酯、乙酸異丙酯、乙酸丁酯、己烷、庚烷、辛烷、壬烷、癸烷、十一烷、十二烷、環己烷、甲基環己烷、鹵化烴、丙酮、甲基乙基酮、甲基異丁基酮、環己酮、二甲基甲醯胺、二甲基亞碸、N-甲基吡咯啶酮等。 In addition, it is also possible to use other solvents which have low water solubility or are not water soluble. Agents, for example: benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , heptane, octane, decane, decane, undecane, dodecane, cyclohexane, methylcyclohexane, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, ring Hexanone, dimethylformamide, dimethylhydrazine, N-methylpyrrolidone and the like.

顏料的微細化步驟中使用的溶劑可僅為1種，亦可視需要將2種以上混合使用。 The solvent used in the step of miniaturizing the pigment may be used alone or in combination of two or more kinds as needed.

顏料的微細化步驟中使用的水溶性無機鹽可列舉：氯化鈉、氯化鉀、氯化鈣、氯化鋇、硫酸鈉等。 The water-soluble inorganic salt used in the step of refining the pigment may, for example, be sodium chloride, potassium chloride, calcium chloride, barium chloride or sodium sulfate.

微細化步驟中的水溶性無機鹽的使用量為顏料的1質量倍~50質量倍，上述水溶性無機鹽的使用量多的微細化步驟具有磨碎效果，但就生產性的方面而言，更佳的量為顏料的1質量倍~10質量倍。另外，較佳為使用水分為1%以下的無機鹽類。 The water-soluble inorganic salt used in the refining step is used in an amount of from 1 to 50 times by mass of the pigment, and the refining step in which the amount of the water-soluble inorganic salt used is large has a grinding effect, but in terms of productivity, A more preferable amount is 1 mass to 10 mass times of the pigment. Further, it is preferred to use an inorganic salt having a water content of 1% or less.

相對於顏料100質量份，微細化步驟中的水溶性有機溶劑的使用量為50質量份至300質量份的範圍，較佳為100質量份至200質量份的範圍。 The amount of the water-soluble organic solvent used in the miniaturization step is in the range of 50 parts by mass to 300 parts by mass, preferably 100 parts by mass to 200 parts by mass, based on 100 parts by mass of the pigment.

對顏料的微細化步驟中的濕式粉碎裝置的運轉條件並無特別限制，為了有效地利用粉碎介質進行磨碎，在裝置為捏合機的情況下的運轉條件為：裝置內的刀片的轉速較佳為10 rpm~200 rpm，並且雙軸的旋轉比相對較大的裝置的磨碎效果大而較佳。運轉時間較佳為與乾式粉碎時間合併為1小時~8小時，裝置 的內溫較佳為50℃~150℃。另外，作為粉碎介質的水溶性無機鹽的粉碎粒度為5 μm~50 μm，粒徑的分布為急劇的，且較佳為球形。 The operating conditions of the wet pulverizing apparatus in the step of miniaturizing the pigment are not particularly limited, and in order to effectively grind using the pulverizing medium, the operating condition in the case where the apparatus is a kneading machine is: the rotation speed of the blade in the apparatus is higher It is preferably 10 rpm to 200 rpm, and the rotation of the two shafts is larger than that of the relatively large device. The running time is preferably combined with the dry pulverization time to be 1 hour to 8 hours, the device The internal temperature is preferably from 50 ° C to 150 ° C. Further, the water-soluble inorganic salt as the pulverization medium has a pulverized particle size of 5 μm to 50 μm, and the distribution of the particle diameter is sharp, and is preferably spherical.

有色材料組成物中的綠色顏料與特定染料的組成比以質量換算計，較佳為1：1~10：1，尤佳為2：1~10：1。藉由設為該範圍，可將特定染料對綠色顏料表面的吸附率設為特定染料的15質量%以上，能夠發揮本發明的效果。 The composition ratio of the green pigment to the specific dye in the colored material composition is preferably 1:1 to 10:1, and particularly preferably 2:1 to 10:1. By setting it as the range, the adsorption rate of the specific dye on the surface of the green pigment can be made 15% by mass or more of the specific dye, and the effect of the present invention can be exhibited.

另外，相對於有色材料組成物的總質量，有色材料組成物中的顏料與染料的總和較佳為10質量%~60質量%。 Further, the total of the pigment and the dye in the colored material composition is preferably from 10% by mass to 60% by mass based on the total mass of the colored material composition.

(分散組成物的製造方法) (Manufacturing method of dispersed composition)

分散組成物是使用後述的(F)有機溶劑將綠色顏料與特定染料進行分散而獲得。此時，較佳為使用上述有色材料組成物來代替綠色顏料與特定染料。 The dispersion composition is obtained by dispersing a green pigment and a specific dye using an organic solvent (F) described later. At this time, it is preferred to use the above-described colored material composition instead of the green pigment and the specific dye.

進而，分散組成物中可添加後述的分散劑、顏料衍生物、以及其他成分，亦可添加綠色顏料以外的顏料。 Further, a dispersant, a pigment derivative, and other components to be described later may be added to the dispersion composition, and a pigment other than the green pigment may be added.

本發明的分散組成物可藉由如下方式而獲得：將上述各成分總括或者分期添加，使用例如縱型或者橫型的砂磨機、針磨機、狹縫磨機、超音波分散機等分散機，利用0.01 mm~1 mm粒徑的由玻璃、氧化鋯等形成的珠粒來進行微分散處理。 The dispersion composition of the present invention can be obtained by adding or substituting each of the above components, and using, for example, a vertical or horizontal sand mill, a pin mill, a slit mill, an ultrasonic disperser or the like. The machine is microdispersed by using beads of glass, zirconia or the like having a particle diameter of 0.01 mm to 1 mm.

在預先不進行預混合而不經過有色材料組成物，將綠色顏料與特定染料進行分散時，較佳為在顏料的分散過程中將染料 投入於分散裝置內，特佳為在分散的初期階段投入。該情況下，若一下子大量投入染料，則容易形成結塊而欠佳，因此較佳為緩緩投入。 When the green pigment is dispersed with a specific dye without pre-mixing without passing through the colored material composition, it is preferred to dye the dye during the dispersion of the pigment. It is put into the dispersion apparatus, and it is especially preferable to invest in the initial stage of dispersion. In this case, if a large amount of dye is added at once, it is easy to form agglomerates and it is not preferable, so it is preferable to introduce them slowly.

另外，在將特定染料添加於分散裝置內的情況下，可添加特定染料的染料溶液，但就溶解性等方面而言，若可能，則較佳為以固體狀態投入。在以染料溶液來添加的情況下，亦較佳為添加後的染料濃度儘可能高的狀態。其原因在於，分散組成物的系統中的染料越為濃度高的狀態，越促進對顏料的吸附，結果越容易達成本發明的效果(即耐熱性提高)。就該觀點而言，染料的添加較佳為在分散初期(分散開始時)進行，在使用後述的多階段分散的情況下，較佳為在第1階段的分散的初期進行。 Further, when a specific dye is added to the dispersion device, a dye solution of a specific dye may be added. However, in terms of solubility and the like, it is preferably added in a solid state if possible. In the case of adding as a dye solution, it is also preferred that the dye concentration after the addition is as high as possible. The reason for this is that the higher the concentration of the dye in the system in which the composition is dispersed, the more the adsorption of the pigment is promoted, and as a result, the effect of the present invention (i.e., the heat resistance is improved) is more easily achieved. From this point of view, the addition of the dye is preferably carried out at the initial stage of dispersion (at the start of dispersion), and in the case of using a multistage dispersion described later, it is preferably carried out in the initial stage of dispersion in the first stage.

作為染料溶液的製備方法，可於染料中投入有機溶劑進行攪拌，但就容易溶解的方面而言，較佳為於正在攪拌的有機溶劑中投入粉體染料的方法。染料的投入方法可總括地投入全部量，亦可分期投入。 As a method of preparing the dye solution, an organic solvent may be added to the dye to stir, but in terms of being easily dissolved, a method of introducing a powder dye into an organic solvent being stirred is preferred. The method of inputting the dye can be used in a total amount, and can be input in stages.

作為染料的溶解方法，可使用棒狀物將上述包含染料與有機溶劑的溶液進行攪拌，亦可使用磁力攪拌器，另外，只要利用使螺旋槳狀的攪拌子在容器內以一定速度朝一個方向旋轉的通常攪拌機進行溶解即可。另外，亦可利用混合機(mixer)、溶解器(dissolver)等施加剪切力來溶解。視需要亦可加溫而溶解。 As a method of dissolving the dye, a solution containing the dye and the organic solvent may be stirred using a rod, or a magnetic stirrer may be used, and the propeller-like stirrer may be rotated in one direction at a constant speed in the container. Usually the mixer is dissolved. Further, it may be dissolved by applying a shear force using a mixer, a dissolver or the like. It can also be heated and dissolved as needed.

另外，亦可在利用珠粒進行微分散之前，使用二輥機、 三輥機、球磨機、轉筒篩磨機、分散機、捏合機、雙向捏合機、均質機、摻合機、單軸或雙軸的擠出機等，一邊賦予強的剪切力一邊進行混練處理。 In addition, it is also possible to use a two-roller before using the beads for microdispersion. Three-roller, ball mill, drum screen mill, disperser, kneader, two-way kneader, homogenizer, blender, single-axis or twin-axis extruder, etc., while imparting strong shear force while mixing deal with.

此外，關於混練、分散的詳情記載於T.C.Patton著「塗料流動與顏料分散(Paint Flow and Pigment Dispersion)」(1964年，約翰威利兄弟(John Wiley and Sons)公司刊)等中，本發明中亦可應用其中記載的方法。 Further, details of the kneading and dispersion are described in "Attuit Flow and Pigment Dispersion" by TCPatton (John Wiley and Sons, 1964), and the like. The methods described therein can also be applied.

進而，分散中，如下方法亦為較佳實施方式：在分散初期將分散組成物中的固體成分設定為高於最終分散組成物的固體成分來進行分散，且在接近分散的最終的時刻，利用有機溶劑或其他高分子化合物等著色成分以外的成分進行稀釋。 Further, in the dispersion, the following method is also a preferred embodiment in which the solid content in the dispersion composition is set to be higher than the solid content of the final dispersion composition at the initial stage of dispersion, and is dispersed at a final timing close to the dispersion. The components other than the coloring component such as an organic solvent or another polymer compound are diluted.

該分散組成物的製備方法典型而言，分成粗分散與精密分散的2階段、或者進一步分為多階段來實施分散的方法亦為較佳實施方式。 The method for preparing the dispersion composition is generally a preferred embodiment in which the dispersion is divided into two stages of coarse dispersion and precise dispersion, or further divided into a plurality of stages to carry out dispersion.

即較佳為，當將分散初期的分散組成物中的特定染料的濃度設為Ci，且將分散結束後的分散組成物中的特定染料的濃度(在分散結束後進行濃度調整的情況下，為濃度調整後的特定染料的濃度)設為Cf時，以滿足Ci>Cf的關係的方式，基於2階段以上的步驟來分散。 In other words, when the concentration of the specific dye in the dispersion composition at the initial stage of dispersion is Ci, and the concentration of the specific dye in the dispersion composition after the dispersion is completed (when the concentration is adjusted after the dispersion is completed, When the concentration of the specific dye after the concentration adjustment is Cf, the method of two-stage or more is dispersed so as to satisfy the relationship of Ci>Cf.

在實施預混合的情況下，Ci為預混合中的特定染料的濃度；在不實施預混合的情況下，Ci為2階段分散或多階段分散中 第1階段的分散(2階段分散中為粗分散)中的特定染料的濃度；在不進行預混合而是以1階段進行分散的情況下，Ci為分散開始時刻的特定染料的濃度。另外，Cf為分散的最終階段(2階段分散中為精密分散)中的特定染料的濃度，在分散後進行濃度調整的情況下，濃度調整後的特定染料的濃度相當於上述Cf。 In the case of performing premixing, Ci is the concentration of the specific dye in the premixing; in the case where the premixing is not carried out, Ci is in the 2-stage dispersion or multistage dispersion The concentration of the specific dye in the dispersion of the first stage (the coarse dispersion in the two-stage dispersion); and the dispersion in the first stage without pre-mixing, Ci is the concentration of the specific dye at the start of dispersion. Further, Cf is the concentration of the specific dye in the final stage of dispersion (precise dispersion in the two-stage dispersion), and when the concentration is adjusted after dispersion, the concentration of the specific dye after the concentration adjustment corresponds to the above Cf.

藉由上述方式，在高濃度下不僅染料更容易吸附於顏料表面，而且在進行顏料分散的同時，染料緩緩地吸附於顏料表面而達成吸附平衡，同時進行分散，因此可提高吸附率。若為Ci=Cf，則即便最終進行上述濃度調整，亦由於自投入時起染料濃度已經低，故而達成吸附平衡需要花費時間，根據情況，由於由分散劑或添加劑引起的吸附阻礙而存在最終的吸附率降低的可能性，因此欠佳。 According to the above manner, at a high concentration, not only the dye is more easily adsorbed on the surface of the pigment, but also the pigment is slowly adsorbed on the surface of the pigment while the pigment is dispersed, and the adsorption equilibrium is achieved, and the dispersion is carried out, so that the adsorption rate can be improved. If Ci=Cf, even if the concentration adjustment is finally carried out, since the dye concentration is already low since the time of the input, it takes time to reach the adsorption equilibrium, and depending on the case, there is a final hindrance due to the adsorption inhibition by the dispersant or the additive. The possibility of a decrease in the adsorption rate is therefore poor.

另外，依據該方法，在分散初期由於固體成分大，故而對分散液施加高剪切力，藉由該剪切而容易進行顏料的分散，獲得高分散性，故而為較佳實施方式。 Further, according to this method, since the solid content is large at the initial stage of dispersion, high shear force is applied to the dispersion liquid, and the pigment is easily dispersed by the shearing to obtain high dispersibility, which is a preferred embodiment.

另外，Ci較佳為設定為Cf的1.1倍~10倍，尤佳為1.1倍~5倍。藉由設為該範圍，能夠容易獲得具有高分散性的分散組成物。 Further, Ci is preferably set to 1.1 times to 10 times Cf, and particularly preferably 1.1 times to 5 times. By setting it as this range, the dispersion composition with high dispersibility can be acquired easily.

(分散組成物中所含的其他成分) (other components contained in the dispersed composition)

以下，對本發明的分散組成物中較佳包含的分散劑、顏料衍生物進行說明。 Hereinafter, a dispersant and a pigment derivative which are preferably contained in the dispersion composition of the present invention will be described.

(分散劑) (Dispersant)

作為分散劑，具體而言可使用多種化合物，例如可列舉：有機矽氧烷聚合物KP341(信越化學工業(股)製造)，(甲基)丙烯酸系(共)聚合物Polyflow No.75、Polyflow No.90、Polyflow No.95(共榮社化學工業(股)製造)，W001(裕商(股)公司製造)等陽離子系界面活性劑；聚氧乙烯月桂醚、聚氧乙烯硬脂醚、聚氧乙烯油醚、聚氧乙烯辛基苯醚、聚氧乙烯壬基苯醚、聚乙二醇二月桂酸酯、聚乙二醇二硬脂酸酯、山梨糖醇脂肪酸酯等非離子系界面活性劑；W004、W005、W017(裕商(股)公司製造)等陰離子系界面活性劑；EFKA-46、EFKA-47、EFKA-47EA、EFKA POLYMER 100、EFKA POLYMER 400、EFKA POLYMER 401、EFKA POLYMER 450(均由汽巴精化公司製造)，Disperse Aid 6、Disperse Aid 8、Disperse Aid 15、Disperse Aid 9100(均由聖諾普科(San Nopco)公司製造)等高分子分散劑；Solsperse 3000、Solsperse 5000、Solsperse 9000、Solsperse 12000、Solsperse 13240、Solsperse 13940、Solsperse 17000、Solsperse 24000、Solsperse 26000、Solsperse 28000等各種Solsperse分散劑(日本路博潤(股)公司製造)；Adeka Pluronic L31、Adeka Pluronic F38、Adeka Pluronic L42、Adeka Pluronic L44、Adeka Pluronic L61、Adeka Pluronic L64、Adeka Pluronic F68、Adeka Pluronic L72、Adeka Pluronic P95、Adeka Pluronic F77、Adeka Pluronic P84、Adeka Pluronic F87、Adeka Pluronic P94、Adeka Pluronic L101、Adeka Pluronic P103、Adeka Pluronic F108、Adeka Pluronic L121、Adeka Pluronic P-123(旭電化(股)製造)及Eonet S-20(三洋化成(股)製造)，Disperbyk 101、Disperbyk 103、Disperbyk 106、Disperbyk 108、Disperbyk 109、Disperbyk 111、Disperbyk 112、Disperbyk 116、Disperbyk 130、Disperbyk 140、Disperbyk 142、Disperbyk 162、Disperbyk 163、Disperbyk 164、Disperbyk 166、Disperbyk 167、Disperbyk 170、Disperbyk 171、Disperbyk 174、Disperbyk 176、Disperbyk 180、Disperbyk 182、Disperbyk 2000、Disperbyk 2001、Disperbyk 2050、Disperbyk 2150(畢克化學(BYK-CHEMIE)公司製造)。 Specific examples of the dispersing agent include a plurality of compounds, and examples thereof include an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic (co) polymer Polyflow No. 75, and Polyflow. No. 90, Polyflow No. 95 (manufactured by Kyoeisha Chemical Industry Co., Ltd.), W001 (manufactured by Yusei Co., Ltd.) and other cationic surfactants; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Non-ionics such as polyoxyethylene ether ether, polyoxyethylene octyl phenyl ether, polyoxyethylene decyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitol fatty acid ester Interface activator; anionic surfactant such as W004, W005, W017 (manufactured by Yushang Co., Ltd.); EFKA-46, EFKA-47, EFKA-47EA, EFKA POLYMER 100, EFKA POLYMER 400, EFKA POLYMER 401, EFKA POLYMER 450 (both manufactured by Ciba Specialty Chemicals Co., Ltd.), disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (all manufactured by San Nopco) and other polymer dispersants; Solsperse 3000, Solsperse 5000, Solsperse 9000, Solsperse 12000, Solsperse 13240, So Various Solsperse dispersants (made by Lubrizol Corporation, USA) such as lsperse 13940, Solsperse 17000, Solsperse 24000, Solsperse 26000, Solsperse 28000; Adeka Pluronic L31, Adeka Pluronic F38, Adeka Pluronic L42, Adeka Pluronic L44, Adeka Pluronic L61 , Adeka Pluronic L64, Adeka Pluronic F68, Adeka Pluronic L72, Adeka Pluronic P95, Adeka Pluronic F77, Adeka Pluronic P84, Adeka Pluronic F87, Adeka Pluronic P94, Adeka Pluronic L101, Adeka Pluronic P103, Adeka Pluronic F108, Adeka Pluronic L121, Adeka Pluronic P-123 (made by Asahi Kasei Co., Ltd.) and Eonet S-20 (made by Sanyo Chemical Co., Ltd.), Disperbyk 101, Disperbyk 103, Disperbyk 106, Disperbyk 108, Disperbyk 109, Disperbyk 111, Disperbyk 112, Disperbyk 116, Disperbyk 130, Disperbyk 140, Disperbyk 142, Disperbyk 162, Disperbyk 163, Disperbyk 164, Disperbyk 166, Disperbyk 167, Disperbyk 170 , Disperbyk 171, Disperbyk 174, Disperbyk 176, Disperbyk 180, Disperbyk 182, Disperbyk 2000, Disperbyk 2001, Disperbyk 2050, Disperbyk 2150 (manufactured by BYK-CHEMIE).

-高分子分散劑- - Polymer Dispersant -

本發明的分散組成物較佳為包含下述記載的高分子分散劑作為分散劑。 The dispersion composition of the present invention preferably contains a polymer dispersant described below as a dispersant.

本發明的分散組成物較佳為含有具有下述通式(II)或下述通式(III)所表示的結構單元的至少1種、具有酸基的結構單元的至少1種的高分子化合物(以下有時稱為「特定聚合物」)。 The dispersion composition of the present invention is preferably a polymer compound containing at least one structural unit having at least one structural unit represented by the following formula (II) or the following formula (III) and having an acid group; (The following is sometimes referred to as "specific polymer").

上述通式(II)及通式(III)中，R1~R6分別獨立地表示氫原子或者一價有機基，X1及X2分別獨立地表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或者伸苯基，L1及L2分別獨立地表示單鍵或者二價有機連結基，A1及A2分別獨立地表示一價有機基，m及n分別獨立地表示2~8的整數，p及q分別獨立地表示1~100的整數。 In the above formula (II) and formula (III), R 1 to R 6 each independently represent a hydrogen atom or a monovalent organic group, and X 1 and X 2 each independently represent -CO-, -C(=O). O-, -CONH-, -OC(=O)- or a phenyl group, and L 1 and L 2 each independently represent a single bond or a divalent organic linking group, and A 1 and A 2 each independently represent a monovalent organic group. m and n each independently represent an integer of 2 to 8, and p and q each independently represent an integer of 1 to 100.

(通式(II)或通式(III)所表示的結構單元) (structural unit represented by the general formula (II) or the general formula (III))

上述通式(II)或通式(III)所表示的結構單元作為重複單元而包含於(A)高分子化合物中。 The structural unit represented by the above formula (II) or formula (III) is contained as a repeating unit in (A) a polymer compound.

上述通式(II)及通式(III)中，R1~R6分別獨立地表示氫原子或者一價有機基。一價有機基較佳為經取代或未經取代的烷基。烷基較佳為碳數1~12的烷基，更佳為碳數1~8的烷基，特佳為碳數1~4的烷基。 In the above formula (II) and formula (III), R 1 to R 6 each independently represent a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a substituted or unsubstituted alkyl group. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms.

在烷基具有取代基的情況下，該取代基例如可列舉羥基、烷氧基(較佳為碳數1~5，更佳為碳數1~3)、甲氧基、乙氧基、環己氧基等。 In the case where the alkyl group has a substituent, the substituent may, for example, be a hydroxyl group or an alkoxy group (preferably having a carbon number of 1 to 5, more preferably a carbon number of 1 to 3), a methoxy group, an ethoxy group or a ring. Hexyloxy and the like.

具體而言，較佳的烷基例如可列舉：甲基、乙基、丙基、正丁基、異丁基、第三丁基、正己基、環己基、2-羥基乙基、3- 羥基丙基、2-羥基丙基、2-甲氧基乙基。 Specific examples of preferred alkyl groups include methyl, ethyl, propyl, n-butyl, isobutyl, tert-butyl, n-hexyl, cyclohexyl, 2-hydroxyethyl, 3- Hydroxypropyl, 2-hydroxypropyl, 2-methoxyethyl.

R1、R2、R4及R5較佳為氫原子，就對顏料表面的吸附效率的方面而言，R3及R6最佳為氫原子或者甲基。 R 1 , R 2 , R 4 and R 5 are preferably a hydrogen atom, and R 3 and R 6 are preferably a hydrogen atom or a methyl group in terms of the adsorption efficiency on the surface of the pigment.

X1及X2分別獨立地表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-、或者伸苯基。其中，就對顏料的吸附性的觀點而言，較佳為-C(=O)O-、-CONH-、伸苯基，最佳為-C(=O)O-。 X 1 and X 2 each independently represent -CO-, -C(=O)O-, -CONH-, -OC(=O)-, or a phenyl group. Among them, from the viewpoint of the adsorptivity of the pigment, -C(=O)O-, -CONH-, and a phenyl group are preferable, and -C(=O)O- is preferable.

L1及L2分別獨立地表示單鍵或者二價有機連結基。二價有機連結基較佳為經取代或未經取代的伸烷基、或由該伸烷基與雜原子或者包含雜原子的部分結構所形成的二價有機連結基。此處，伸烷基較佳為碳數1~12的伸烷基，尤佳為碳數1~8的伸烷基，特佳為碳數1~4的伸烷基。另外，包含雜原子的部分結構中的雜原子例如可列舉氧原子、氮原子、硫原子，其中，較佳為氧原子、氮原子。 L 1 and L 2 each independently represent a single bond or a divalent organic linking group. The divalent organic linking group is preferably a substituted or unsubstituted alkylene group, or a divalent organic linking group formed by the alkylene group and a hetero atom or a partial structure containing a hetero atom. Here, the alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, particularly preferably an alkylene group having 1 to 8 carbon atoms, particularly preferably an alkylene group having 1 to 4 carbon atoms. Further, examples of the hetero atom in the partial structure containing a hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom. Among them, an oxygen atom and a nitrogen atom are preferable.

具體而言，較佳的伸烷基例如可列舉：亞甲基、伸乙基、伸丙基、三亞甲基、四亞甲基。 Specific examples of preferred alkylene groups include methylene, ethyl, propyl, trimethylene, and tetramethylene.

在伸烷基具有取代基的情況下，該取代基例如可列舉羥基等。 In the case where the alkylene group has a substituent, the substituent may, for example, be a hydroxyl group or the like.

就對顏料的吸附性的方面而言，二價有機連結基較佳為在上述伸烷基的末端具有選自由-C(=O)-、-OC(=O)-、-NHC(=O)-所組成組群中的雜原子或者包含雜原子的部分結構，且經由該雜原子或者包含雜原子的部分結構而與鄰接的氧原子連結的基團。 In terms of the adsorption property to the pigment, the divalent organic linking group preferably has a terminal selected from the group consisting of -C(=O)-, -OC(=O)-, -NHC(=O) at the terminal end of the alkylene group. a hetero atom in a group or a partial structure containing a hetero atom, and a group bonded to an adjacent oxygen atom via the hetero atom or a partial structure containing a hetero atom.

A1及A2分別獨立地表示一價有機基。一價有機基較佳為經取代或未經取代的烷基、或者經取代或未經取代的芳基。 A 1 and A 2 each independently represent a monovalent organic group. The monovalent organic group is preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

較佳的烷基的例子可列舉碳原子數為1至20的直鏈狀、分支狀及環狀烷基，其具體例可列舉：甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十六烷基、十八烷基、二十烷基、異丙基、異丁基、第二丁基、第三丁基、異戊基、新戊基、1-甲基丁基、異己基、2-乙基己基、2-甲基己基、環己基、環戊基、2-降莰基。 Examples of preferred alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Hexyl, heptyl, octyl, decyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl Base, second butyl, tert-butyl, isopentyl, neopentyl, 1-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, cyclohexyl, cyclopentyl, 2 - Lowering the base.

經取代的烷基的取代基是使用去除氫的一價非金屬原子團的基團，較佳例子可列舉：鹵素原子(-F、-Br、-Cl、-I)、羥基、烷氧基、芳氧基、巰基、烷硫基、芳硫基、烷基二硫基、芳基二硫基、胺基、N-烷基胺基、N,N-二烷基胺基、N-芳基胺基、N,N-二芳基胺基、N-烷基-N-芳基胺基、醯氧基、胺甲醯氧基、N-烷基胺甲醯氧基、N-芳基胺甲醯氧基、N,N-二烷基胺甲醯氧基、N,N-二芳基胺甲醯氧基、N-烷基-N-芳基胺甲醯氧基、烷基亞碸基、芳基亞碸基、醯氧基、醯硫基、醯基胺基、N-烷基醯基胺基、N-芳基醯基胺基、脲基、N'-烷基脲基、N',N'-二烷基脲基、N'-芳基脲基、N',N'-二芳基脲基、N'-烷基-N'-芳基脲基、N-烷基脲基、N-芳基脲基、N'-烷基-N-烷基脲基、N'-烷基-N-芳基脲基、N',N'-二烷基-N-烷基脲基、N',N'-二烷基-N-芳基脲基、N'-芳基-N-烷基脲基、N'-芳基-N-芳基脲基、N',N'-二芳基-N-烷基脲基、N',N'-二 芳基-N-芳基脲基、N'-烷基-N'-芳基-N-烷基脲基、N'-烷基-N'-芳基-N-芳基脲基、烷氧基羰基胺基、芳氧基羰基胺基、N-烷基-N-烷氧基羰基胺基、N-烷基-N-芳氧基羰基胺基、N-芳基-N-烷氧基羰基胺基、N-芳基-N-芳氧基羰基胺基、甲醯基、醯基、羧基、烷氧基羰基、芳氧基羰基、胺甲醯基、N-烷基胺甲醯基、N,N-二烷基胺甲醯基、N-芳基胺甲醯基、N,N-二芳基胺甲醯基、N-烷基-N-芳基胺甲醯基、烷基亞磺醯基、芳基亞磺醯基、烷基磺醯基、芳基磺醯基、磺基(-SO3H)及其共軛鹼基(以下稱為磺酸基)、烷氧基磺醯基、芳氧基磺醯基、胺亞磺醯基(sulfinamoyl)、N-烷基胺亞磺醯基、N,N-二烷基胺亞磺醯基、N-芳基胺亞磺醯基、N,N-二芳基胺亞磺醯基、N-烷基-N-芳基胺亞磺醯基、胺磺醯基、N-烷基胺磺醯基、N,N-二烷基胺磺醯基、N-芳基胺磺醯基、N,N-二芳基胺磺醯基、N-烷基-N-芳基胺磺醯基、磷醯基(phosphono)(-PO3H2)及其共軛鹼基(以下稱為磷酸基)、二烷基磷醯基(-PO3(alkyl)2)、二芳基磷醯基(-PO3(aryl)2)、烷基芳基磷醯基(-PO3(alkyl)(aryl))、單烷基磷醯基(-PO3H(alkyl))及其共軛鹼基(以下稱為烷基磷酸基)、單芳基磷醯基(-PO3H(aryl))及其共軛鹼基(以下稱為芳基磷酸基)、磷醯基氧基(-OPO3H2)及其共軛鹼基(以下稱為磷酸基氧基)、二烷基磷醯基氧基(-OPO3(alkyl)2)、二芳基磷醯基氧基(-OPO3(aryl)2)、烷基芳基磷醯基氧基(-OPO3(alkyl)(aryl))、單烷基磷醯基氧基 (-OPO3H(alkyl))及其共軛鹼基(以下稱為烷基磷酸基氧基)、單芳基磷醯基氧基(-OPO3H(aryl))及其共軛鹼基(以下稱為芳基磷酸基氧基)、氰基、硝基、芳基、雜芳基、烯基、炔基、矽烷基。 The substituent of the substituted alkyl group is a group using a monovalent non-metal atomic group from which hydrogen is removed, and preferred examples thereof include a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, Aryloxy, fluorenyl, alkylthio, arylthio, alkyldithio, aryldithio, amine, N-alkylamino, N,N-dialkylamino, N-aryl Amino, N,N-diarylamine, N-alkyl-N-arylamine, decyloxy, aminemethyloxy, N-alkylamine, methoxy, N-arylamine Methoxy, N,N-dialkylamine, methoxy, N,N-diarylamine, methoxy, N-alkyl-N-arylamine, methoxy, alkyl , aryl sulfhydryl, decyloxy, decylthio, decylamino, N-alkyldecylamino, N-aryldecylamino, ureido, N'-alkylureido, N',N'-dialkylureido, N'-arylureido, N',N'-diarylureido, N'-alkyl-N'-arylureido, N-alkyl Urea, N-arylureido, N'-alkyl-N-alkylureido, N'-alkyl-N-arylureido, N',N'-dialkyl-N-alkyl Urea, N', N'-dialkyl-N-arylureido, N'-aryl-N-alkylureido, N'-aryl-N-arylureido, N', N '-two Aryl-N-alkylureido, N',N'-diaryl-N-arylureido, N'-alkyl-N'-aryl-N-alkylureido, N'-alkane -N'-aryl-N-arylureido, alkoxycarbonylamino, aryloxycarbonylamino, N-alkyl-N-alkoxycarbonylamino, N-alkyl-N- Aryloxycarbonylamino, N-aryl-N-alkoxycarbonylamino, N-aryl-N-aryloxycarbonylamino, decyl, decyl, carboxy, alkoxycarbonyl, aryl Oxycarbonyl, amine, mercapto, N-alkylamine, mercapto, N,N-dialkylamine, mercapto, N-arylamine, mercapto, N,N-diarylamine , N-alkyl-N-arylaminecarbamyl, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, sulfo (-SO 3 H) and Its conjugated base (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylamine sulfinyl group, N, N -dialkylamine sulfinyl, N-arylamine sulfinyl, N,N-diarylamine sulfinyl, N-alkyl-N-arylamine sulfinyl, amine sulfonate Sulfhydryl, N-alkylamine sulfonyl, N,N-dialkylamine sulfonyl, N-arylamine sulfonyl, N,N-diarylamine Acyl, N- alkyl -N- sulfo acyl aryl amines, phosphorus-acyl (phosphono) (- PO 3 H 2) and its conjugate base (hereinafter referred to as phosphoric acid group), acyl dialkylphosphoryl (-PO 3 (alkyl) 2 ), diarylphosphonium (-PO 3 (aryl) 2 ), alkyl aryl phosphonyl (-PO 3 (alkyl) (aryl), monoalkyl phosphonium (PO 3 H(alkyl)) and its conjugated base (hereinafter referred to as alkyl phosphate group), monoarylphosphonium group (-PO 3 H (aryl)) and its conjugated base (hereinafter referred to as An aryl phosphate group, a phosphonyloxy group (-OPO 3 H 2 ) and a conjugated base thereof (hereinafter referred to as a phosphoryloxy group), a dialkylphosphonium oxy group (-OPO 3 (alkyl) 2 ), diarylphosphonyloxy (-OPO 3 (aryl) 2 ), alkyl aryl phosphonyloxy (-OPO 3 (alkyl) (aryl), monoalkylphosphoniumoxy (-OPO 3 H(alkyl)) and its conjugated base (hereinafter referred to as alkylphosphooxy), monoarylphosphoniumoxy (-OPO 3 H(aryl)) and its conjugated base (hereinafter referred to as arylphosphooxy), cyano, nitro, aryl, heteroaryl, alkenyl, alkynyl, decylalkyl.

該些取代基中的烷基的具體例可列舉上述烷基，該些烷基可進一步具有取代基。 Specific examples of the alkyl group in the substituents include the above alkyl groups, and the alkyl groups may further have a substituent.

就分散穩定性的方面而言，取代基較佳為烷氧基、芳氧基、烷硫基、芳硫基、N,N-二烷基胺基、N,N-二芳基胺基、N-烷基-N-芳基胺基、醯氧基、芳基、雜芳基、烯基、炔基、矽烷基。 In terms of dispersion stability, the substituent is preferably an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an N,N-dialkylamino group, an N,N-diarylamino group, N-alkyl-N-arylamino, decyloxy, aryl, heteroaryl, alkenyl, alkynyl, decylalkyl.

芳基的具體例可列舉：苯基、聯苯基、萘基、甲苯基、二甲苯基、均三甲苯基(mesityl)、異丙苯基(cumenyl)、氯苯基、溴苯基、氯甲基苯基、羥基苯基、甲氧基苯基、乙氧基苯基、苯氧基苯基、乙醯氧基苯基、苯甲醯氧基苯基、甲基硫苯基、苯基硫苯基、甲基胺基苯基、二甲基胺基苯基、乙醯基胺基苯基、羧基苯基、甲氧基羰基苯基、乙氧基苯基羰基、苯氧基羰基苯基、N-苯基胺甲醯基苯基、苯基、氰基苯基、磺基苯基、磺酸基苯基、磷醯基苯基、磷酸基苯基等。 Specific examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a chlorophenyl group, a bromophenyl group, and a chlorine group. Methylphenyl, hydroxyphenyl, methoxyphenyl, ethoxyphenyl, phenoxyphenyl, ethoxylated phenyl, benzhydryloxyphenyl, methylthiophenyl, phenyl Thiophenyl, methylaminophenyl, dimethylaminophenyl, ethenylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, ethoxyphenylcarbonyl, phenoxycarbonylbenzene A group, N-phenylamine, mercaptophenyl, phenyl, cyanophenyl, sulfophenyl, sulfophenyl, phosphonylphenyl, phenylphenyl, and the like.

就分散穩定性及顯影性的方面而言，A1及A2較佳為碳原子數1至20的直鏈狀烷基、碳原子數3至20的分支狀烷基、以及碳原子數5至20的環狀烷基，更佳為碳原子數4至15的直鏈狀烷基、碳原子數4至15的分支狀烷基、以及碳原子數6至10的環狀烷基，尤佳為碳原子數6至10的直鏈狀烷基、碳原子數6 至12的分支狀烷基。 In terms of dispersion stability and developability, A 1 and A 2 are preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, and 5 carbon atoms. The cyclic alkyl group to 20 is more preferably a linear alkyl group having 4 to 15 carbon atoms, a branched alkyl group having 4 to 15 carbon atoms, and a cyclic alkyl group having 6 to 10 carbon atoms. It is preferably a linear alkyl group having 6 to 10 carbon atoms or a branched alkyl group having 6 to 12 carbon atoms.

m及n分別獨立地表示2~8的整數。就分散穩定性及顯影性的方面而言，m及n較佳為4~6，最佳為5。 m and n each independently represent an integer of 2-8. In terms of dispersion stability and developability, m and n are preferably 4 to 6, and most preferably 5.

p及q分別獨立地表示1~100的整數。p不同者、q不同者可混合2種以上。就分散穩定性及顯影性的方面而言，p及q較佳為5~60，更佳為5~40，尤佳為5~20。 p and q each independently represent an integer from 1 to 100. Two or more types may be mixed with different p and different q. In terms of dispersion stability and developability, p and q are preferably from 5 to 60, more preferably from 5 to 40, and still more preferably from 5 to 20.

本發明的特定聚合物包含上述通式(II)所表示的結構單元的至少1種或者上述通式(III)所表示的結構單元的至少1種，或者包含上述通式(II)所表示的結構單元的至少1種以及上述通式(III)所表示的結構單元的至少1種。此處，上述通式(II)及通式(III)中，以下組合為特佳的實施方式。即，R1、R2、R4及R5較佳為氫原子，R3及R6較佳為氫原子或者甲基。X1及X2較佳為-C(=O)O-。L1及L2較佳為在碳數1~4的伸烷基的末端具有選自由-C(=O)-、-OC(=O)-、-NHC(=O)-所組成組群中的雜原子或者包含雜原子的部分結構，且經由該雜原子或者包含雜原子的部分結構而與鄰接的氧原子連結的二價有機連結基。m及n較佳為5，p及q較佳為5~20。 The specific polymer of the present invention contains at least one of the structural units represented by the above formula (II) or at least one of the structural units represented by the above formula (III), or contains the formula represented by the above formula (II). At least one of the structural units and at least one of the structural units represented by the above formula (III). Here, in the above formula (II) and formula (III), the following combinations are particularly preferred embodiments. That is, R 1 , R 2 , R 4 and R 5 are preferably a hydrogen atom, and R 3 and R 6 are preferably a hydrogen atom or a methyl group. X 1 and X 2 are preferably -C(=O)O-. L 1 and L 2 preferably have a group selected from the group consisting of -C(=O)-, -OC(=O)-, -NHC(=O)- at the terminal of the alkylene group having 1 to 4 carbon atoms. A hetero atom or a partial structure containing a hetero atom, and a divalent organic linking group bonded to an adjacent oxygen atom via the hetero atom or a partial structure containing a hetero atom. m and n are preferably 5, and p and q are preferably 5-20.

就分散穩定性的方面而言，本發明的特定聚合物較佳為包含上述通式(II)所表示的結構單元的至少1種的聚合物。 The specific polymer of the present invention is preferably a polymer containing at least one structural unit represented by the above formula (II) in terms of dispersion stability.

另外，上述通式(II)所表示的結構單元更佳為下述通式(II)-2所表示的結構單元。 Further, the structural unit represented by the above formula (II) is more preferably a structural unit represented by the following formula (II)-2.

上述通式(II)-2中，R1~R3分別獨立地表示氫原子或者一價有機基，La表示碳數2~10的伸烷基，Lb表示-C(=O)-或者-NHC(=O)-，A1表示一價有機基，m表示2~8的整數，p表示1~100的整數。 In the above formula (II)-2, R 1 to R 3 each independently represent a hydrogen atom or a monovalent organic group, La represents an alkylene group having 2 to 10 carbon atoms, and Lb represents -C(=O)- or - NHC(=O)-, A 1 represents a monovalent organic group, m represents an integer of 2-8, and p represents an integer of 1 to 100.

R1~R3、A1所表示的一價有機基以及m、p的詳情及較佳實施方式與上述通式(II)中的情況相同。 The details and preferred embodiments of the monovalent organic group represented by R 1 to R 3 and A 1 and m and p are the same as those in the above formula (II).

La更佳為碳數2~8的伸烷基，尤佳為碳數2~4的伸烷基。具體而言，例如可列舉：伸乙基、伸丙基、三亞甲基、四亞甲基。在伸烷基具有取代基的情況下，該取代基例如可列舉羥基等。 La is more preferably an alkylene group having 2 to 8 carbon atoms, and particularly preferably an alkylene group having 2 to 4 carbon atoms. Specific examples thereof include an ethyl group, a propyl group, a trimethylene group, and a tetramethylene group. In the case where the alkylene group has a substituent, the substituent may, for example, be a hydroxyl group or the like.

上述通式(II)、通式(III)或通式(II)-2所表示的結構單元分別藉由使下述通式(i)、通式(ii)或通式(i)-2所表示的單體進行聚合或者共聚合而作為高分子化合物的重複單元來導入。 The structural unit represented by the above formula (II), formula (III) or formula (II)-2 is represented by the following formula (i), formula (ii) or formula (i)-2, respectively. The monomer shown is subjected to polymerization or copolymerization and introduced as a repeating unit of the polymer compound.

上述通式(i)、通式(ii)及通式(i)-2中，R1~R6分別獨立地表示氫原子或者一價有機基，X1及X2分別獨立地表示-CO-、-C(=O)O-、-CONH-、-OC(=O)-或者伸苯基，L1及L2分別獨立地表示單鍵或者二價有機連結基，La表示碳數2~10的伸烷基，Lb表示-C(=O)-或者-NHC(=O)-，A1及A2分別獨立地表示一價有機基，m及n分別獨立地表示2~8的整數，p及q分別獨立地表示1~100的整數。 In the above formula (i), formula (ii) and formula (i)-2, R 1 to R 6 each independently represent a hydrogen atom or a monovalent organic group, and X 1 and X 2 each independently represent -CO. -, -C(=O)O-, -CONH-, -OC(=O)- or phenyl group, L 1 and L 2 each independently represent a single bond or a divalent organic linking group, and La represents a carbon number of 2 ~10 alkylene, Lb represents -C(=O)- or -NHC(=O)-, A 1 and A 2 each independently represent a monovalent organic group, and m and n each independently represent 2-8 The integers, p and q, respectively, represent integers from 1 to 100, respectively.

R1~R6、X1及X2、L1及L2、A1及A2、m及n、p及q與上述通式(II)、通式(III)及通式(II)-2含義相同。 R 1 to R 6 , X 1 and X 2 , L 1 and L 2 , A 1 and A 2 , m and n, p and q and the above formula (II), formula (III) and formula (II) -2 has the same meaning.

以下，列舉通式(i)、通式(ii)或通式(i)-2所表示的單體的較佳具體例[單體(A-1)~單體(A-24)]，但本發明並不限定於該些具體例。 Hereinafter, preferred examples of the monomer represented by the general formula (i), the general formula (ii) or the general formula (i)-2 [monomer (A-1) to monomer (A-24)], However, the present invention is not limited to these specific examples.

本發明的特定聚合物包含上述通式(II)或通式(III)所表示的結構單元的至少1種，可僅包含1種，亦可包含2種以上。 The specific polymer of the present invention contains at least one of the structural units represented by the above formula (II) or (III), and may be contained alone or in combination of two or more.

另外，特定聚合物中，上述通式(II)或通式(III)所表示的結構單元的含量並無特別限制，在將聚合物中所含的總結構單元設為100質量%的情況下，就兼具顏料的分散性及顯影性的方面而言，較佳為含有5質量%以上的上述結構單元，更佳為含有30質量%以上，尤佳為含有40質量%~60質量%。 In addition, the content of the structural unit represented by the above formula (II) or formula (III) is not particularly limited, and in the case where the total structural unit contained in the polymer is 100% by mass, In view of the dispersibility and developability of the pigment, the above-mentioned structural unit is preferably contained in an amount of 5% by mass or more, more preferably 30% by mass or more, and particularly preferably 40% by mass to 60% by mass.

(具有酸基的結構單元) (structural unit having an acid group)

本發明的特定聚合物包含具有酸基的結構單元(含酸基的結構單元)。含酸基的結構單元的酸基對顏料或者顏料衍生物發揮作為吸附基的作用。 The specific polymer of the present invention contains a structural unit having an acid group (a structural unit containing an acid group). The acid group of the acid group-containing structural unit functions as an adsorption group for the pigment or the pigment derivative.

本發明的含酸基的結構單元中，酸基較佳為pKa為10以下的酸基。pKa為10以下的酸基的具體例例如可列舉磺酸基、磷酸基、羧酸基、苯酚基等。其中，就兼具顏料分散性與顯影性的觀點而言，最適宜使用羧酸基。 In the acid group-containing structural unit of the present invention, the acid group is preferably an acid group having a pKa of 10 or less. Specific examples of the acid group having a pKa of 10 or less include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, and a phenol group. Among them, a carboxylic acid group is most preferably used from the viewpoint of having both pigment dispersibility and developability.

本發明的含酸基的結構單元中，酸基可直接結合於特定聚合物的主鏈上，亦可經由連結鏈而結合於特定聚合物的主鏈上。 In the acid group-containing structural unit of the present invention, the acid group may be directly bonded to the main chain of the specific polymer, or may be bonded to the main chain of the specific polymer via the linking chain.

將特定聚合物的主鏈與酸基連結的連結鏈較佳為包含選自芳香環、醚基、酯基、醯胺基、脲基及/或胺基甲酸酯基中的官能基的連結基。上述官能基由於其自身對顏料顯示吸附性，故而認為在含酸基的結構單元中，若上述官能基位於接近酸基的位置，則具有增加對顏料或者顏料衍生物的吸附性的效果。 The linked chain linking the main chain of the specific polymer to the acid group is preferably a linker containing a functional group selected from the group consisting of an aromatic ring, an ether group, an ester group, a decylamino group, a urea group, and/or a urethane group. base. Since the functional group exhibits adsorptivity to the pigment by itself, it is considered that in the structural unit containing an acid group, when the functional group is located close to the acid group, the effect of increasing the adsorption property to the pigment or the pigment derivative is obtained.

此處，所謂特定聚合物的主鏈，是指合成聚合物時藉由聚合而連結的部位，例如，若為將甲基丙烯酸酯聚合而成的聚合物，則是指甲基丙烯醯基部位藉由聚合而連結的伸烷基部位。 Here, the main chain of a specific polymer means a site which is bonded by polymerization when a polymer is synthesized. For example, a polymer obtained by polymerizing a methacrylate means a methyl methacrylate moiety. An alkyl group attached by polymerization.

另外，上述連結基可將多種連結基組合使用。例如可將芳香環與醚基、芳香環與酯基、芳香環與脲基、醚基與脲基、芳香環與醚基及脲基等組合使用。 Further, the above-mentioned linking group can be used in combination of a plurality of linking groups. For example, an aromatic ring and an ether group, an aromatic ring and an ester group, an aromatic ring and a urea group, an ether group and a urea group, an aromatic ring and an ether group, and a urea group can be used in combination.

在本發明的分散組成物含有鈦黑作為顏料的情況下，由 於鈦黑具有氮原子，故而較佳為使用氫結合性官能基作為特定聚合物的連結基，具體而言，較佳為使用醯胺基、脲基、胺基甲酸酯基。 In the case where the dispersion composition of the present invention contains titanium black as a pigment, Since titanium black has a nitrogen atom, it is preferred to use a hydrogen-bonding functional group as a linking group of a specific polymer. Specifically, a mercapto group, a urea group or a urethane group is preferably used.

另外，本發明的含酸基的結構單元中使用的連結基較佳為導入芳香環。藉由連結鏈具有芳香環，與通常的烷基鏈等相比，可藉由立體阻礙來減少聚合物的纏繞，芳香環容易從主鏈部朝向聚合物之外，因此可提高顏料的分散性。 Further, it is preferred that the linking group used in the acid group-containing structural unit of the present invention is introduced into an aromatic ring. By having an aromatic ring in the linking chain, the entanglement of the polymer can be reduced by steric hindrance as compared with a usual alkyl chain or the like, and the aromatic ring is easily directed from the main chain portion toward the polymer, thereby improving the dispersibility of the pigment. .

此處，所謂芳香環，表示具有π電子的原子排列成環狀的結構，可使用苯環、萘環、蒽環等不含雜原子的環，或吡啶環、吡咯環、呋喃環、咔唑環、噻吩環等包含雜原子的環等各種環。其中，可適宜使用通用性高的苯環、萘環、吡啶環，可更適宜使用苯環，更佳為下述式(2)所表示的結構。 Here, the aromatic ring means a structure in which atoms having π electrons are arranged in a ring shape, and a ring containing no hetero atom such as a benzene ring, a naphthalene ring or an anthracene ring, or a pyridine ring, a pyrrole ring, a furan ring or a carbazole can be used. Various rings such as a ring containing a hetero atom such as a ring or a thiophene ring. Among them, a benzene ring, a naphthalene ring, and a pyridine ring having high versatility can be suitably used, and a benzene ring can be more preferably used, and a structure represented by the following formula (2) is more preferable.

上述式(2)中，Y表示與特定聚合物的主鏈的連結基，S表示酸性官能基。R表示氫原子、可具有取代基的烷基、可具有 取代基的芳基、可具有取代基的烷氧基、可具有取代基的芳氧基、可具有取代基的雜芳氧基、可具有取代基的烷氧基羰基、可具有取代基的芳氧基羰基、可具有取代基的烷基醯胺基、可具有取代基的芳基醯胺基、鹵素基、硝基。另外，n表示0至4的整數，m表示1至5的整數。 In the above formula (2), Y represents a linking group to a main chain of a specific polymer, and S represents an acidic functional group. R represents a hydrogen atom, an alkyl group which may have a substituent, and may have An aryl group of a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a heteroaryloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, and a aryl group which may have a substituent An oxycarbonyl group, an alkylguanamine group which may have a substituent, an arylguanamine group which may have a substituent, a halogen group, and a nitro group. Further, n represents an integer of 0 to 4, and m represents an integer of 1 to 5.

上述式(2)中，Y表示與特定聚合物的主鏈的連結基。連結基的結構並無特別限定，就降低酸基的pKa的觀點而言，較佳為以吸電子基來連結苯環與主鏈，尤佳為以酯基、醯胺基、磺醯胺基等來連結，更佳為以酯基連結。 In the above formula (2), Y represents a linking group to a main chain of a specific polymer. The structure of the linking group is not particularly limited. From the viewpoint of lowering the pKa of the acid group, it is preferred to bond the benzene ring and the main chain with an electron-withdrawing group, and more preferably an ester group, a guanamine group or a sulfonamide group. It is more preferable to link by an ester group.

以下表示Y的較佳具體例，但Y並不限定於該些結構。X表示與特定聚合物的主鏈結合的部位，Z表示與苯環結合的部位。 Preferred specific examples of Y are shown below, but Y is not limited to these structures. X represents a site to which a main polymer is bonded, and Z represents a site to which a benzene ring is bonded.

上述式(2)中，R表示氫原子、可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烷氧基、可具有取代基的芳氧基、可具有取代基的雜芳氧基、可具有取代基的烷氧基羰基、可具有取代基的芳氧基羰基、可具有取代基的烷基醯胺基、可具有取代基的芳基醯胺基、鹵素基、硝基。就降低酸基的pKa的觀點而言，較佳為經氫原子或吸電子基所取代，且較佳為氫原子、可具有取代基的烷氧基羰基、可具有取代基的芳氧基羰基、可具 有取代基的烷基醯胺基、可具有取代基的芳基醯胺基、鹵素基、硝基、羧基，進一步尤佳為氫原子、可具有取代基的烷氧基羰基、可具有取代基的芳氧基羰基。 In the above formula (2), R represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, may have a substituent Heteroaryloxy group, alkoxycarbonyl group which may have a substituent, aryloxycarbonyl group which may have a substituent, alkyl guanylamino group which may have a substituent, aryl guanylamino group which may have a substituent, a halogen group Nitro. From the viewpoint of lowering the pKa of the acid group, it is preferably a hydrogen atom or an electron withdrawing group, and is preferably a hydrogen atom, an alkoxycarbonyl group which may have a substituent, and an aryloxycarbonyl group which may have a substituent. Can be The alkylamino group having a substituent, the arylguanamine group which may have a substituent, a halogen group, a nitro group, a carboxyl group, further preferably a hydrogen atom, an alkoxycarbonyl group which may have a substituent, may have a substituent Aryloxycarbonyl.

本發明的含酸基的結構單元較佳為具有羧酸基作為酸基的結構單元(以下有時稱為「含羧酸基的結構單元」)。更佳為具有經由包含除氫原子以外的原子數為4個以上的原子團的連結鏈而結合於特定聚合物的主鏈上的羧酸基的結構單元。 The acid group-containing structural unit of the present invention is preferably a structural unit having a carboxylic acid group as an acid group (hereinafter sometimes referred to as "a structural unit containing a carboxylic acid group"). More preferably, it is a structural unit having a carboxylic acid group bonded to a main chain of a specific polymer via a linking chain containing an atomic group having four or more atoms other than a hydrogen atom.

上述含羧酸基的結構單元中，羧酸基經由連結鏈而結合於主鏈上，藉此羧酸基部分的可撓性提高，可更有效率地與顏料或者顏料衍生物相互作用。另外，羧酸基亦發揮作為顯影性基的作用，因此可撓性提高，藉此顯影性亦提高。就該方面而言，連結鏈越長越佳。 In the structural unit containing a carboxylic acid group, a carboxylic acid group is bonded to the main chain via a linking chain, whereby the flexibility of the carboxylic acid group portion is improved, and the pigment or the pigment derivative can be more efficiently interacted. Further, since the carboxylic acid group also functions as a developable group, the flexibility is improved, and the developability is also improved. In this respect, the longer the link chain, the better.

另一方面，若連結鏈過長，則可導入至聚合物中的含羧酸基的結構單元的數量變少，因此進而，可導入至聚合物中的羧酸基的數量變少。 On the other hand, when the linking chain is too long, the number of structural units containing a carboxylic acid group which can be introduced into the polymer is small, and therefore, the amount of the carboxylic acid group which can be introduced into the polymer is small.

根據上述情況，含羧酸基的結構單元中，較佳為將主鏈與羧酸基連結的連結鏈包含除氫原子以外的原子數為4個至100個的原子團，更佳為包含除氫原子以外的原子數為6個至60個的原子團，尤佳為包含除氫原子以外的原子數為8個至20個的原子團。 According to the above, in the structural unit containing a carboxylic acid group, it is preferred that the linking chain linking the main chain and the carboxylic acid group contains an atomic group having 4 to 100 atoms other than the hydrogen atom, and more preferably contains hydrogen. The number of atoms other than the atom is 6 to 60, and it is particularly preferable to contain an atomic group having 8 to 20 atoms other than the hydrogen atom.

上述含羧酸基的結構單元中，將特定聚合物的主鏈與羧 酸基連結的連結鏈的較佳實施方式與所述的含酸基的結構單元中的連結鏈相同，另外，亦同樣可將多種連結基組合使用來作為連結鏈。 In the above structural unit containing a carboxylic acid group, the main chain of the specific polymer and the carboxy group A preferred embodiment of the acid-linked linking chain is the same as the linking chain in the acid group-containing structural unit, and a plurality of linking groups may be used in combination as a linking chain.

上述含羧酸基的結構單元中使用的連結基與所述的含酸基的結構單元相同，較佳為導入芳香環，芳香環的較佳實施方式亦相同。 The linking group used in the structural unit containing a carboxylic acid group is the same as the structural unit containing the acid group, and it is preferred to introduce an aromatic ring. The preferred embodiment of the aromatic ring is also the same.

上述含羧酸基的結構單元的部分結構更佳為下述式(1)所表示的結構。 The partial structure of the above structural unit containing a carboxylic acid group is more preferably a structure represented by the following formula (1).

上述式(1)中，Y、R、及n與上述式(2)含義相同。羧酸基可經由連結基而從苯環導入。 In the above formula (1), Y, R, and n have the same meanings as in the above formula (2). The carboxylic acid group can be introduced from the benzene ring via a linking group.

以下表示上述式(1)所表示的部分結構的具體例，但該部分結構並不限定於該些具體例。X表示與主鏈的結合部位。 Specific examples of the partial structure represented by the above formula (1) are shown below, but the partial structure is not limited to these specific examples. X represents a binding site to the main chain.

上述含羧酸基的結構單元中，較佳為上述連結鏈包含具有芳香環、且除氫原子以外的原子數為6個以上60個以下的原子團。更佳為上述芳香環為苯環，且經由該苯環或者以酯鍵而結合於主鏈上的連結鏈。 In the structural unit containing a carboxylic acid group, it is preferred that the linking chain includes an atomic group having an aromatic ring and having 6 or more and 60 or less atoms other than a hydrogen atom. More preferably, the aromatic ring is a benzene ring, and is bonded to the main chain via the benzene ring or an ester bond.

本發明的特定聚合物中，就抑制在形成著色區域時顯影液中生成析出物的方面而言，上述含羧酸基的結構單元的含量較佳為50 mgKOH/g以上。為了有效抑制生成顏料的一次粒子的凝聚體(即二次凝聚體)，或者有效削弱二次凝聚體的凝聚力，含羧 酸基的結構單元的含量較佳為50 mgKOH/g~200 mgKOH/g。 In the specific polymer of the present invention, the content of the carboxylic acid group-containing structural unit is preferably 50 mgKOH/g or more in terms of suppressing the formation of precipitates in the developer in the formation of the colored region. In order to effectively suppress the aggregate of the primary particles forming the pigment (ie, secondary aggregates), or to effectively weaken the cohesive force of the secondary aggregates, the carboxyl group is contained. The content of the structural unit of the acid group is preferably from 50 mgKOH/g to 200 mgKOH/g.

(其他結構單元) (other structural units)

出於提高對顏料的吸附性的目的，本發明的特定聚合物較佳為使具有可吸附於顏料上的官能基的單體進一步共聚合而成的高分子化合物。 The specific polymer of the present invention is preferably a polymer compound obtained by further copolymerizing a monomer having a functional group adsorbable on the pigment for the purpose of improving the adsorption property to the pigment.

除酸基以外，具有可吸附於顏料上的官能基的單體具體而言可列舉：具有有機色素結構或者雜環結構的單體、具有鹼性氮原子的單體、具有離子性基的單體等。其中，就對顏料的吸附力的方面而言，較佳為具有有機色素結構或者雜環結構的單體。 In addition to the acid group, the monomer having a functional group which can be adsorbed on the pigment may specifically be a monomer having an organic dye structure or a heterocyclic structure, a monomer having a basic nitrogen atom, and a single having an ionic group. Body and so on. Among them, in terms of the adsorption force to the pigment, a monomer having an organic dye structure or a heterocyclic structure is preferred.

具有可吸附於顏料上的官能基的單體(monomer)可根據所分散的顏料的種類來適當選擇，該些單體可單獨使用，亦可併用2種以上。 The monomer having a functional group that can be adsorbed on the pigment can be appropriately selected depending on the type of the pigment to be dispersed, and these monomers may be used singly or in combination of two or more kinds.

本發明的特定聚合物可在不損及其效果的範圍內，更包含源自可共聚合的乙烯系單體的結構單元。 The specific polymer of the present invention may further contain a structural unit derived from a copolymerizable vinyl monomer, within a range not impairing the effect thereof.

此處可使用的乙烯系單體並無特別限制，例如較佳為：(甲基)丙烯酸酯類、丁烯酸酯類、乙烯酯類、順丁烯二酸二酯類、反丁烯二酸二酯類、亞甲基丁二酸二酯類、(甲基)丙烯醯胺類、乙烯醚類、乙烯醇的酯類、苯乙烯類、(甲基)丙烯腈等。此種乙烯系單體的具體例例如可列舉如下所述的化合物。此外，本說明書中在表示「丙烯醯基、甲基丙烯醯基」的任一者或者兩者的情況下有時記載為「(甲基)丙烯醯基」。 The vinyl monomer which can be used herein is not particularly limited, and for example, preferred are (meth)acrylates, butenoates, vinyl esters, maleic acid diesters, and antibutene. Acid diesters, methylene succinic acid diesters, (meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile, and the like. Specific examples of such a vinyl monomer include the following compounds. In addition, in the case of either or both of "acryloyl methacrylic acid and methacryl fluorenyl group", it may be described as "(meth)acryl fluorenyl group".

(甲基)丙烯酸酯類的例子可列舉：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸第三丁基環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸第三辛酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸十八烷基酯、(甲基)丙烯酸乙醯氧基乙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-(2-甲氧基乙氧基)乙酯、(甲基)丙烯酸3-苯氧基-2-羥基丙酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸二乙二醇單甲醚、(甲基)丙烯酸二乙二醇單***、(甲基)丙烯酸三乙二醇單甲醚、(甲基)丙烯酸三乙二醇單***、(甲基)丙烯酸聚乙二醇單甲醚、(甲基)丙烯酸聚乙二醇單***、(甲基)丙烯酸β-苯氧基乙氧基乙酯、(甲基)丙烯酸壬基苯氧基聚乙二醇、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基)丙烯酸三氟乙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸全氟辛基乙酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸三溴苯基氧基乙酯等。 Examples of the (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate Cyclohexyl ester, 2-ethylhexyl (meth)acrylate, third octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, (A) Ethyl ethoxide ethyl acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethyl (meth) acrylate Oxyethyl ester, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, Diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl (meth)acrylate, (meth)acrylic acid polyethylene glycol monomethyl ether, (meth)acrylic acid poly Glycol monoethyl ether, β-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, (methyl) Dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, tribromophenyl (meth)acrylate, tribromophenyloxyethyl (meth)acrylate, and the like.

丁烯酸酯類的例子可列舉：丁烯酸丁酯、及丁烯酸己酯等。 Examples of the butenoate esters include butyl butenoate and hexyl butenoate.

乙烯酯類的例子可列舉：乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、甲氧基乙酸乙烯酯、及苯甲酸乙烯酯等。 Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, and vinyl benzoate.

順丁烯二酸二酯類的例子可列舉：順丁烯二酸二甲酯、順丁烯二酸二乙酯、及順丁烯二酸二丁酯等。 Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

反丁烯二酸二酯類的例子可列舉：反丁烯二酸二甲酯、反丁烯二酸二乙酯、及反丁烯二酸二丁酯等。 Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

亞甲基丁二酸二酯類的例子可列舉：亞甲基丁二酸二甲酯、亞甲基丁二酸二乙酯、及亞甲基丁二酸二丁酯等。 Examples of the methylene succinic acid diesters include dimethyl methylene succinate, diethyl methylene succinate, and dibutyl methylene succinate.

(甲基)丙烯醯胺類可列舉：(甲基)丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-丙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-正丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-環己基(甲基)丙烯醯胺、N-(2-甲氧基乙基)(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-苯基(甲基)丙烯醯胺、N-苄基(甲基)丙烯醯胺、(甲基)丙烯醯基嗎啉、二丙酮丙烯醯胺等。 Examples of the (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-propyl (methyl). Acrylamide, N-isopropyl (meth) acrylamide, N-n-butyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-cyclohexyl ( Methyl) acrylamide, N-(2-methoxyethyl)(methyl) acrylamide, N,N-dimethyl(meth) decylamine, N,N-diethyl (A Base) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) propylene hydrazino, diacetone acrylamide, and the like.

乙烯醚類的例子可列舉：甲基乙烯醚、丁基乙烯醚、己基乙烯醚、及甲氧基乙基乙烯醚等。 Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

苯乙烯類的例子可列舉：苯乙烯、甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、異丙基苯乙烯、丁基苯乙烯、羥基苯乙烯、甲氧基苯乙烯、丁氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙烯、二氯苯乙烯、溴苯乙烯、氯甲基苯乙烯、以可利用酸性物質而去保護(deprotection)的基團(例如第三丁氧基羰基(t-butoxycarbonyl，t-Boc)等)來保護的羥基苯乙烯、乙烯基 苯甲酸甲酯、及α-甲基苯乙烯等。 Examples of the styrenes include styrene, methyl styrene, dimethyl styrene, trimethylstyrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxystyrene, and methoxy. Styrene, butoxy styrene, ethoxylated styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, a group deprotected with an acidic substance (eg, t-butoxycarbonyl (t-Boc), etc.) to protect hydroxystyrene, vinyl Methyl benzoate, and α-methylstyrene.

本發明的特定聚合物的具體例可列舉以下的例示化合物1~例示化合物35。 Specific examples of the specific polymer of the present invention include the following exemplified compound 1 to exemplified compound 35.

本發明的特定聚合物的較佳分子量以重量平均分子量(Mw)計為5000~100000的範圍，以數量平均分子量(Mn)計為2500~50000的範圍。更佳為以重量平均分子量(Mw)計為 10000~50000的範圍，以數量平均分子量(Mn)計為5000~30000的範圍。尤其最佳為以重量平均分子量(Mw)計為20000~40000的範圍，以數量平均分子量(Mn)計為5000~20000的範圍。 The preferred molecular weight of the specific polymer of the present invention is in the range of 5,000 to 100,000 in terms of weight average molecular weight (Mw) and in the range of 2,500 to 50,000 in terms of number average molecular weight (Mn). More preferably in terms of weight average molecular weight (Mw) The range of 10,000 to 50,000 is in the range of 5,000 to 30,000 in terms of the number average molecular weight (Mn). In particular, it is preferably in the range of 20,000 to 40,000 in terms of weight average molecular weight (Mw) and in the range of 5,000 to 20,000 in terms of number average molecular weight (Mn).

即，就有效地解開顏料的一次粒子的凝聚體(即二次凝聚體)，或者有效削弱再凝聚的觀點而言，特定聚合物的重量平均分子量(Mw)較佳為1000以上。另外，就利用含有分散組成物的著色感光性組成物來製造彩色濾光片時的顯影性的觀點而言，特定聚合物的重量平均分子量(Mw)較佳為50000以下。 That is, the weight average molecular weight (Mw) of the specific polymer is preferably 1,000 or more from the viewpoint of effectively dissolving the aggregate of the primary particles of the pigment (that is, the secondary aggregate) or effectively weakening the re-agglomeration. In addition, the weight average molecular weight (Mw) of the specific polymer is preferably 50,000 or less from the viewpoint of developability when producing a color filter using a colored photosensitive composition containing a dispersion composition.

本發明的特定聚合物可利用通常的自由基聚合法來製造。 The specific polymer of the present invention can be produced by a usual radical polymerization method.

通常使用懸浮聚合法或者溶液聚合法等。合成上述特定聚合物時所使用的溶劑例如可列舉：二氯乙烷、環己酮、甲基乙基酮、丙酮、甲醇、乙醇、丙醇、丁醇、乙二醇單甲醚、乙二醇單***、乙酸2-甲氧基乙酯、1-甲氧基-2-丙醇、乙酸1-甲氧基-2-丙酯、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、二甲基亞碸、甲苯、乙酸乙酯、乳酸甲酯、乳酸乙酯等。該些溶劑可單獨使用或將2種以上混合使用。此外，自由基聚合時可使用自由基聚合起始劑，另外，進而可使用鏈轉移劑(例：2-巰基乙醇及十二烷基硫醇)。 A suspension polymerization method or a solution polymerization method or the like is usually used. Examples of the solvent used in the synthesis of the above specific polymer include dichloroethane, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, and ethylene. Alcohol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N,N-dimethylformamide, N,N - dimethyl acetamide, dimethyl hydrazine, toluene, ethyl acetate, methyl lactate, ethyl lactate, and the like. These solvents may be used singly or in combination of two or more. Further, a radical polymerization initiator may be used in the radical polymerization, and a chain transfer agent (for example, 2-mercaptoethanol and dodecylmercaptan) may be further used.

分散劑在分散組成物中的含量較佳為顏料：特定聚合物(質量比)=1：0.1~1：2的範圍，更佳為1：0.2~1：1的範圍， 尤佳為1：0.4~1：0.7的範圍。 The content of the dispersant in the dispersion composition is preferably a range of a pigment: a specific polymer (mass ratio) = 1:0.1 to 1:2, more preferably a range of 1:0.2 to 1:1. It is especially suitable for the range of 1:0.4 to 1:0.7.

另外，分散組成物可含有顏料衍生物。 Further, the dispersion composition may contain a pigment derivative.

所謂顏料衍生物，是指在有機顏料的側鏈上導入有酸性基、鹼性基、芳香族基作為取代基的化合物，與特定染料不同。 The term "pigment derivative" refers to a compound in which an acidic group, a basic group, or an aromatic group is introduced as a substituent in a side chain of an organic pigment, and is different from a specific dye.

本發明中，綠色顏料將特定染料吸附於其表面，尚可藉由使具有與上述特定聚合物(高分子分散劑)具有親和性的部位的顏料衍生物，吸附於未吸附有特定染料的顏料表面，將其用作特定聚合物的吸附點，從而使顏料進一步作為微細粒子而分散於著色組成物中。另外，亦可防止其再凝聚。即，顏料衍生物藉由對未吸附有特定染料的顏料表面進行改質，而具有促進本發明的特定聚合物之類的高分子分散劑的吸附的效果。 In the present invention, the green pigment adsorbs a specific dye on the surface thereof, and is adsorbed to a pigment which does not adsorb a specific dye by a pigment derivative having a portion having affinity with the above specific polymer (polymer dispersant). The surface is used as a point of adsorption of a specific polymer, whereby the pigment is further dispersed as fine particles in the coloring composition. In addition, it can also prevent re-agglomeration. That is, the pigment derivative has an effect of promoting adsorption of a polymer dispersant such as a specific polymer of the present invention by modifying the surface of the pigment to which the specific dye is not adsorbed.

本發明的特定聚合物具有酸基，因此藉由使用具有鹼性基的鹼性顏料衍生物作為顏料衍生物，則顏料的分散性進一步提高，可有效地分散微細顏料。而且，藉由使用含有鹼性顏料衍生物的著色感光性組成物，可進而形成色濃度不均小且色特性優異的彩色濾光片。 Since the specific polymer of the present invention has an acid group, by using a basic pigment derivative having a basic group as a pigment derivative, the dispersibility of the pigment is further improved, and the fine pigment can be efficiently dispersed. Further, by using the colored photosensitive composition containing a basic pigment derivative, a color filter having small color density unevenness and excellent color characteristics can be further formed.

顏料衍生物是以有機顏料作為母體骨架，且在側鏈上導入酸性基或鹼性基、芳香族基作為取代基的化合物。具體而言，成為母體骨架的有機顏料可列舉：喹吖啶酮(quinacridone)系顏料、酞花青系顏料、偶氮系顏料、喹啉黃(quinophthalone)系顏料、異吲哚啉(isoindoline)系顏料、異吲哚啉酮(isoindolinone) 系顏料、喹啉(quinoline)顏料、二酮吡咯并吡咯(diketopyrrolopyrrole)顏料、苯并咪唑酮(benzimidazolone)顏料等。另外，作為母體骨架，亦包含通常不稱為色素的萘系、蒽醌系、三嗪系、喹啉系等淡黃色的芳香族多環化合物。 The pigment derivative is a compound in which an organic pigment is used as a matrix and an acidic group or a basic group or an aromatic group is introduced as a substituent in a side chain. Specifically, examples of the organic pigment to be the matrix of the parent include quinacridone pigment, phthalocyanine pigment, azo pigment, quinophthalone pigment, and isoindoline. Pigment, isoindolinone A pigment, a quinoline pigment, a diketopyrrolopyrrole pigment, a benzimidazolone pigment, or the like. Further, the parent skeleton also contains a pale yellow aromatic polycyclic compound such as a naphthalene, an anthracene, a triazine or a quinoline which is not normally referred to as a dye.

顏料衍生物可使用以下專利文獻中記載的顏料衍生物：日本專利特開平11-49974號公報、日本專利特開平11-189732號公報、日本專利特開平10-245501號公報、日本專利特開2006-265528號公報、日本專利特開平8-295810號公報、日本專利特開平11-199796號公報、日本專利特開2005-234478號公報、日本專利特開2003-240938號公報、日本專利特開2001-356210號公報等。 For the pigment derivative, the pigment derivative described in the following patent documents can be used: Japanese Patent Laid-Open No. Hei 11-49974, Japanese Patent Laid-Open No. Hei 11-189732, Japanese Patent Laid-Open No. Hei 10-245501, and Japanese Patent Laid-Open Publication No. Hei. Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -356210, etc.

在本發明的分散組成物中使用顏料衍生物的情況下，相對於顏料，該顏料衍生物的使用量較佳為在1質量%~80質量%的範圍內，更佳為在3質量%~65質量%的範圍內，特佳為在5質量%~50質量%的範圍內。若上述含量為該範圍內，則可一邊將黏度抑制為低值，一邊良好地進行顏料的分散，而且可提高分散後的分散穩定性。而且，藉由將該著色感光性組成物應用於製造彩色濾光片，可獲得穿透率高、具有優異的色特性且對比度高的彩色濾光片。 When a pigment derivative is used in the dispersion composition of the present invention, the amount of the pigment derivative used is preferably in the range of 1% by mass to 80% by mass, more preferably 3% by mass based on the pigment. In the range of 65 mass%, it is particularly preferably in the range of 5 mass% to 50 mass%. When the content is within this range, the dispersion of the pigment can be favorably performed while suppressing the viscosity to a low value, and the dispersion stability after dispersion can be improved. Further, by applying the colored photosensitive composition to the production of a color filter, a color filter having high transmittance, excellent color characteristics, and high contrast can be obtained.

進而，在不損及本發明效果的範圍內，視需要，除了本發明的特定聚合物以外，亦可同時使用其他高分子化合物。其他 高分子化合物是使用天然樹脂、改質天然樹脂、合成樹脂、經天然樹脂改質的合成樹脂等。 Further, other polymer compounds may be used in addition to the specific polymer of the present invention, as long as the effects of the present invention are not impaired. other The polymer compound is a synthetic resin which is modified with a natural resin, a modified natural resin, a synthetic resin, or a natural resin.

天然樹脂代表性而言為松香，改質天然樹脂可列舉：松香衍生物、纖維素衍生物、橡膠衍生物、蛋白質衍生物及它們的低聚物。合成樹脂可列舉：環氧樹脂、丙烯酸樹脂、順丁烯二酸樹脂、丁醛樹脂、聚酯樹脂、三聚氰胺(melamine)樹脂、苯酚樹脂、聚胺基甲酸酯樹脂等。經天然樹脂改質的合成樹脂可列舉：松香改質順丁烯二酸樹脂、松香改質苯酚樹脂等。 The natural resin is typically rosin, and examples of the modified natural resin include rosin derivatives, cellulose derivatives, rubber derivatives, protein derivatives, and oligomers thereof. Examples of the synthetic resin include an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. The synthetic resin modified by the natural resin may, for example, be a rosin-modified maleic acid resin or a rosin-modified phenol resin.

合成樹脂可列舉：聚醯胺胺及其鹽、聚羧酸及其鹽、高分子量不飽和酸酯、聚胺基甲酸酯、聚酯、聚(甲基)丙烯酸酯、(甲基)丙烯酸系共聚物、萘磺酸福爾馬林縮合物。 The synthetic resin may, for example, be a polyamine amine and a salt thereof, a polycarboxylic acid and a salt thereof, a high molecular weight unsaturated acid ester, a polyurethane, a polyester, a poly(meth)acrylate, or a (meth)acrylic acid. A copolymer, a formalin condensate of naphthalenesulfonate.

相對於分散組成物的總固體成分(質量)，分散組成物中的綠色顏料的含量較佳為20質量%~70質量%，更佳為30質量%~60質量%。若綠色顏料的含量為上述範圍內，則對於確保色濃度充分優異的色特性而言有效。 The content of the green pigment in the dispersion composition is preferably 20% by mass to 70% by mass, and more preferably 30% by mass to 60% by mass based on the total solid content (mass) of the dispersed composition. When the content of the green pigment is within the above range, it is effective for ensuring color characteristics that are sufficiently excellent in color density.

另外，相對於分散組成物的總固體成分(質量)，分散組成物中的特定染料的含量較佳為5質量%~40質量%，更佳為10質量%~30質量%。若特定染料的含量為上述範圍內，則分散組成物的分散穩定性良好，而且對於確保色濃度充分優異的色特性而言有效。 Further, the content of the specific dye in the dispersion composition is preferably from 5% by mass to 40% by mass, and more preferably from 10% by mass to 30% by mass based on the total solid content (mass) of the dispersed composition. When the content of the specific dye is within the above range, the dispersion stability of the dispersion composition is good, and it is effective for ensuring color characteristics which are sufficiently excellent in color density.

另外，相對於該組成物的總固體成分，本發明的著色感 光性組成物中的綠色顏料的含量較佳為1質量%~50質量%，更佳為1質量%~30質量%。 In addition, the coloring sensation of the present invention is relative to the total solid content of the composition The content of the green pigment in the optical composition is preferably from 1% by mass to 50% by mass, more preferably from 1% by mass to 30% by mass.

進而，相對於該組成物的總固體成分，本發明的著色感光性組成物中的特定染料的含量較佳為0.1質量%~25質量%，更佳為0.1質量%~15質量%。 Further, the content of the specific dye in the colored photosensitive composition of the present invention is preferably from 0.1% by mass to 25% by mass, and more preferably from 0.1% by mass to 15% by mass, based on the total solid content of the composition.

若顏料及特定染料的含量為上述範圍內，則使用著色感光性組成物而獲得的著色層具有高亮度與高對比度，另外，容易滿足顯影性等對著色感光性組成物要求的諸多特性。 When the content of the pigment and the specific dye is within the above range, the coloring layer obtained by using the coloring photosensitive composition has high luminance and high contrast, and it is easy to satisfy various characteristics required for coloring photosensitive composition such as developability.

[(C)聚合性化合物] [(C) Polymerizable Compound]

本發明的著色感光性組成物包含至少一種(C)聚合性化合物。 The colored photosensitive composition of the present invention contains at least one (C) polymerizable compound.

聚合性化合物例如為具有至少一個乙烯性不飽和雙鍵的聚合性化合物，可自公知的構成組成物的成分中選擇使用，可列舉：日本專利特開2006-23696號公報的段落編號[0010]~[0020]中記載的成分、或日本專利特開2006-64921號公報的段落編號[0027]~[0053]中記載的成分。 The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected from known components constituting the composition, and the paragraph number [0010] of JP-A-2006-23696 is exemplified. The components described in [0020] or the components described in paragraphs [0027] to [0053] of JP-A-2006-64921.

另外，使用異氰酸酯與羥基的加成反應而製造的胺基甲酸酯加成的聚合性化合物亦較佳，如日本專利特開昭51-37193號公報、日本專利特公平2-32293號公報、日本專利特公平2-16765號公報中記載的胺基甲酸酯丙烯酸酯類，或日本專利特公昭58-49860號公報、日本專利特公昭56-17654號公報、日本專利特 公昭62-39417號公報、日本專利特公昭62-39418號公報中記載的具有環氧乙烷骨架的胺基甲酸酯化合物類亦較佳。 In addition, a urethane-added polymerizable compound produced by an addition reaction of an isocyanate and a hydroxyl group is also preferred, as disclosed in Japanese Laid-Open Patent Publication No. SHO-51-37193, and Japanese Patent Publication No. 2-32293. The urethane acrylates described in Japanese Patent Publication No. 2-16765, or Japanese Patent Publication No. Sho 58-49860, Japanese Patent Publication No. SHO 56-17654, and Japanese Patent No. A urethane compound having an oxirane skeleton described in JP-A-62-39417, and JP-A-62-39418 is also preferred.

其他例子可列舉：如日本專利特開昭48-64183號公報、日本專利特公昭49-43191號公報、日本專利特公昭52-30490號公報的各公報中記載的聚酯丙烯酸酯類，使環氧樹脂與(甲基)丙烯酸反應而獲得的環氧丙烯酸酯類等多官能丙烯酸酯或甲基丙烯酸酯。進而亦可使用日本黏接協會雜誌第20卷第7期第300頁~第308頁(1984年)中作為光硬化性單體及低聚物來介紹的例子。 Other examples include polyester acrylates described in each of the publications of JP-A-48-64183, JP-A-49-43191, and Japanese Patent Publication No. Sho 52-30490. A polyfunctional acrylate or methacrylate such as an epoxy acrylate obtained by reacting an oxygen resin with (meth)acrylic acid. Further, it can be used as an example of photocurable monomers and oligomers in Japanese Journal of Adhesives, Vol. 20, No. 7, pp. 300-308 (1984).

具體例可列舉以下化合物作為較佳例子：季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、三((甲基)丙烯醯氧基乙基)異氰脲酸酯、季戊四醇四(甲基)丙烯酸酯環氧乙烷(ethylene oxide，EO)改質體、二季戊四醇六(甲基)丙烯酸酯EO改質體等；以及市售品，即NK Ester A-TMMT、NK Ester A-TMM-3、NK Oligo UA-32P、NK Oligo UA-7200(以上由新中村化學工業(股)製造)，Aronix M-305、Aronix M-306、Aronix M-309、Aronix M-450、Aronix M-402、Aronix TO-1382、Aronix TO-2349(以上由東亞合成(股)製造)，V#802(大阪有機化學工業(股)製造)。 Specific examples thereof include the following compounds: pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and three ((Meth) propylene oxiranyl ethyl) isocyanurate, pentaerythritol tetra (meth) acrylate ethylene oxide (EO) modified body, dipentaerythritol hexa (meth) acrylate EO Modified body, etc.; and commercial products, namely NK Ester A-TMMT, NK Ester A-TMM-3, NK Oligo UA-32P, NK Oligo UA-7200 (above manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronix M-402, Aronix TO-1382, Aronix TO-2349 (above manufactured by East Asia Synthetic Co., Ltd.), V#802 (Osaka Organic Chemical industry (stock) manufacturing).

另外，日本專利特開2009-265630號公報的段落編號[0031]~[0061]中記載的化合物亦較佳，其中較佳為[0055]~[0059]中記載的以下化合物。 Further, the compound described in Paragraph Nos. [0031] to [0061] of JP-A-2009-265630 is also preferable, and among them, the following compounds described in [0055] to [0059] are preferable.

該些聚合性化合物可單獨使用，或者將2種以上併用來使用。 These polymerizable compounds may be used singly or in combination of two or more.

著色感光性組成物中的總固體成分中的聚合性化合物的含量(在2種以上的情況下為總含量)較佳為10質量%~80質量%，更佳為15質量%~75質量%，特佳為20質量%~60質量%。 The content of the polymerizable compound in the total solid content in the coloring photosensitive composition (the total content in the case of two or more kinds) is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass. , particularly preferably from 20% by mass to 60% by mass.

[(D)光聚合起始劑] [(D) Photopolymerization initiator]

本發明的著色感光性組成物較佳為含有至少一種光聚 合起始劑。 The colored photosensitive composition of the present invention preferably contains at least one photopolymer Starter.

光聚合起始劑只要是可使上述聚合性化合物進行聚合的起始劑，則並無特別限制，較佳為根據特性、起始效率、吸收波長、獲取性、成本等觀點來選擇。 The photopolymerization initiator is not particularly limited as long as it is an initiator capable of polymerizing the above polymerizable compound, and is preferably selected from the viewpoints of characteristics, initial efficiency, absorption wavelength, availability, cost, and the like.

光聚合起始劑是藉由曝光光而感光，來起始、促進聚合性化合物的聚合的化合物。較佳為對波長為300 nm以上的活性光線產生感應而起始、促進聚合性化合物的聚合的化合物。另外，關於對波長為300 nm以上的活性光線並不直接感應的光聚合起始劑，亦可與增感劑組合而較佳地使用。 The photopolymerization initiator is a compound which initiates and accelerates polymerization of a polymerizable compound by being exposed to light by exposure light. It is preferably a compound which initiates and accelerates polymerization of a polymerizable compound by inducing active light having a wavelength of 300 nm or more. Further, a photopolymerization initiator which does not directly induce active light having a wavelength of 300 nm or more may be preferably used in combination with a sensitizer.

具體而言，例如可列舉：肟酯(oxime ester)化合物、有機鹵化化合物、氧二唑(oxydiazole)化合物、羰基化合物、縮酮(ketal)化合物、安息香(benzoin)化合物、吖啶(acridine)化合物、有機過氧化物、偶氮化合物、香豆素(coumarin)化合物、疊氮(azide)化合物、二茂金屬(metallocene)化合物、六芳基聯咪唑(hexaaryl biimidazole)化合物、有機硼酸化合物、二磺酸化合物、鎓鹽(onium salt)化合物、醯基膦(氧化物)(acyl phosphine(oxide))、二苯甲酮(benzophenone)化合物、苯乙酮(acetophenone)化合物及其衍生物等。 Specific examples thereof include an oxime ester compound, an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, and an acridine compound. , organic peroxide, azo compound, coumarin compound, azide compound, metallocene compound, hexaaryl biimidazole compound, organoboric acid compound, disulfonate An acid compound, an onium salt compound, an acyl phosphine (oxide), a benzophenone compound, an acetophenone compound, and a derivative thereof.

該些化合物中，就感度的方面而言，較佳為肟酯化合物、六芳基聯咪唑化合物。 Among these compounds, an oxime ester compound or a hexaarylbiimidazole compound is preferred in terms of sensitivity.

肟酯化合物可使用以下專利文獻中記載的化合物：日本 專利特開2000-80068號公報、日本專利特開2001-233842號公報、日本專利特表2004-534797號公報、國際公開第2005/080337號、國際公開第2006/018973號說明書、日本專利特開2007-210991號公報、日本專利特開2007-231000號公報、日本專利特開2007-269779號公報、日本專利特開2009-191061號公報、國際公開第2009/131189號說明書。 As the oxime ester compound, a compound described in the following patent documents can be used: Japan Patent Publication No. 2000-80068, Japanese Patent Laid-Open Publication No. 2001-233842, Japanese Patent Laid-Open Publication No. 2004-534797, International Publication No. 2005/080337, International Publication No. 2006/018973, Japanese Patent Laid-Open JP-A-2007-210991, JP-A-2007-231000, JP-A-2007-269779, JP-A-2009-191061, and International Publication No. 2009/131189.

具體的例子可列舉：2-(O-苯甲醯基肟)-1-[4-(苯基硫基)苯基]-1,2-丁二酮、2-(O-苯甲醯基肟)-1-[4-(苯基硫基)苯基]-1,2-戊二酮、2-(O-苯甲醯基肟)-1-[4-(苯基硫基)苯基]-1,2-己二酮、2-(O-苯甲醯基肟)-1-[4-(苯基硫基)苯基]-1,2-庚二酮、2-(O-苯甲醯基肟)-1-[4-(苯基硫基)苯基]-1,2-辛二酮、2-(O-苯甲醯基肟)-1-[4-(甲基苯基硫基)苯基]-1,2-丁二酮、2-(O-苯甲醯基肟)-1-[4-(乙基苯基硫基)苯基]-1,2-丁二酮、2-(O-苯甲醯基肟)-1-[4-(丁基苯基硫基)苯基]-1,2-丁二酮、1-(O-乙醯基肟)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(O-乙醯基肟)-1-[9-甲基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(O-乙醯基肟)-1-[9-丙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(O-乙醯基肟)-1-[9-乙基-6-(2-乙基苯甲醯基)-9H-咔唑-3-基]乙酮、1-(O-乙醯基肟)-1-[9-乙基-6-(2-丁基苯甲醯基)-9H-咔唑-3-基]乙酮等。但並不限定於該些例子。 Specific examples include 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)肟)-1-[4-(phenylthio)phenyl]-1,2-pentanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)benzene 1,1,2-hexanedione, 2-(O-benzylidene fluorenyl)-1-[4-(phenylthio)phenyl]-1,2-heptanedione, 2-(O -benzylidene hydrazide)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 2-(O-benzylidene fluorenyl)-1-[4-(A Phenylthio)phenyl]-1,2-butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(ethylphenylthio)phenyl]-1,2 -butanedione, 2-(O-benzylidene fluorenyl)-1-[4-(butylphenylthio)phenyl]-1,2-butanedione, 1-(O-ethenyl)肟)-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[ 9-Methyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-propyl-6 -(2-methylbenzimidyl)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-ethyl Benzyl hydrazino)-9H-indazol-3-yl]ethanone, 1-(O-ethylindenyl)-1-[9-ethyl-6-(2-butylbenzylidene)- 9H-carbazol-3-yl]ethanone and the like. However, it is not limited to these examples.

另外，本發明中，就感度、隨時間經過的穩定性、耐熱性中的著色的觀點而言，下述通式(A)所表示的化合物亦適宜作 為光聚合起始劑(即肟酯化合物)。 Further, in the present invention, the compound represented by the following formula (A) is also suitable from the viewpoints of sensitivity, stability over time, and coloration in heat resistance. It is a photopolymerization initiator (ie, an oxime ester compound).

通式(A)中，X1、X2及X3分別獨立地表示氫原子、鹵素原子或者烷基，R1表示-R、-OR、-COR、-SR、-CONRR'或者-CN，R2及R3分別獨立地表示-R、-OR、-COR、-SR或者-NRR'。R及R'分別獨立地表示烷基、芳基、芳烷基或者雜環基，該些基團可經選自由鹵素原子及雜環基所組成組群中的1個以上所取代，構成該烷基、及芳烷基中的烷基鏈的碳原子的1個以上可取代為不飽和鍵、醚鍵、或者酯鍵，R及R'可相互結合而形成環。 In the formula (A), X 1 , X 2 and X 3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R 1 represents -R, -OR, -COR, -SR, -CONRR' or -CN. R 2 and R 3 each independently represent -R, -OR, -COR, -SR or -NRR'. R and R' each independently represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and these groups may be substituted by one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more carbon atoms of the alkyl chain in the alkyl group and the aralkyl group may be substituted with an unsaturated bond, an ether bond or an ester bond, and R and R' may be bonded to each other to form a ring.

通式(A)中，在X1、X2及X3表示鹵素原子的情況下的鹵素原子可列舉氟、氯、溴、碘，在X1、X2及X3表示烷基的情況下的烷基例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧 基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、二氟甲基、三氟甲基、三氟乙基、全氟乙基、2-(苯并噁唑-2'-基)乙烯基等。 In the general formula (A), examples of the halogen atom in the case where X 1 , X 2 and X 3 represent a halogen atom include fluorine, chlorine, bromine and iodine, and in the case where X 1 , X 2 and X 3 represent an alkyl group, Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a third pentyl group, and a hexyl group. , heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, Propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, A Oxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole-2'-yl)vinyl, and the like.

其中，較佳為X1、X2及X3均表示氫原子，或者X1表示烷基且X2及X3均表示氫原子。 In particular, it is preferred that X 1 , X 2 and X 3 each represent a hydrogen atom, or X 1 represents an alkyl group and both X 2 and X 3 represent a hydrogen atom.

通式(A)中，R及R'所表示的烷基例如可列舉：甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、第三戊基、己基、庚基、辛基、異辛基、2-乙基己基、第三辛基、壬基、異壬基、癸基、異癸基、乙烯基、烯丙基、丁烯基、乙炔基、丙炔基、甲氧基乙基、乙氧基乙基、丙氧基乙基、甲氧基乙氧基乙基、乙氧基乙氧基乙基、丙氧基乙氧基乙基、甲氧基丙基、單氟甲基、二氟甲基、三氟甲基、三氟乙基、全氟乙基、2-(苯并噁唑-2'-基)乙烯基等。 In the general formula (A), examples of the alkyl group represented by R and R' include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a t-butyl group. Pentyl, isopentyl, third amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, trioctyl, decyl, isodecyl, decyl, isodecyl, ethylene Base, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxy Ethyl, propoxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2-(benzoxazole -2'-yl) vinyl and the like.

R及R'所表示的芳基例如可列舉：苯基、甲苯基、二甲苯基、乙基苯基、氯苯基、萘基、蒽基、菲基等。 Examples of the aryl group represented by R and R' include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a chlorophenyl group, a naphthyl group, an anthracenyl group, and a phenanthryl group.

R及R'所表示的芳烷基例如可列舉：苄基、氯苄基、α-甲基苄基、α,α-二甲基苄基、苯基乙基、苯基乙烯基等。 Examples of the aralkyl group represented by R and R' include a benzyl group, a chlorobenzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, and a phenylvinyl group.

R及R'所表示的雜環基例如可列舉：吡啶基、嘧啶基、呋喃基、硫苯基等。 Examples of the heterocyclic group represented by R and R' include a pyridyl group, a pyrimidinyl group, a furyl group, and a thiophenyl group.

另外，R及R'相互結合而形成的環例如可列舉：哌啶環、嗎啉環等。 Further, examples of the ring formed by bonding R and R' to each other include a piperidine ring and a morpholine ring.

特佳實施方式為包含上述R及R'而構成的R2及R3分別獨立地表示甲基、己基、環己基、-S-Ph、-S-Ph-Cl、及-S-Ph-Br。 In a particularly preferred embodiment, R 2 and R 3 each comprising R and R′ independently represent methyl, hexyl, cyclohexyl, —S—Ph, —S—Ph—Cl, and —S—Ph-Br. .

光聚合起始劑中，特別適合作為光聚合起始劑的是通式(A)中X1、X2及X3均為氫原子者；R1為烷基，特別是甲基者；R2為烷基，特別是甲基者；R3為烷基，特別是乙基者。 Among the photopolymerization initiators, those which are particularly suitable as photopolymerization initiators are those in which X 1 , X 2 and X 3 in the formula (A) are each a hydrogen atom; R 1 is an alkyl group, particularly a methyl group; is alkyl, especially by methyl; R 3 is alkyl, especially ethyl person.

因此，上述通式(A)所表示的光聚合起始劑的較佳具體例可列舉以下所例示的化合物A~化合物F。但，本發明不受以下化合物的任何限制。 Therefore, preferred examples of the photopolymerization initiator represented by the above formula (A) include the compounds A to F exemplified below. However, the present invention is not limited by the following compounds.

通式(A)所表示的光聚合起始劑例如可利用日本專利特開2005-220097號公報中記載的方法來合成。 The photopolymerization initiator represented by the formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.

本發明中使用的通式(A)所表示的化合物是在250 nm~500 nm的波長區域具有吸收波長的化合物。更佳為可列舉在300 nm~380 nm的波長區域具有吸收波長的化合物。特佳為308 nm及355 nm的吸光度高的化合物。 The compound represented by the formula (A) used in the present invention is a compound having an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is a compound having an absorption wavelength in a wavelength range of 300 nm to 380 nm. Particularly preferred are compounds with high absorbance at 308 nm and 355 nm.

另外，本發明中，就感度、隨時間經過的穩定性、後加熱時的著色的觀點而言，作為光聚合起始劑的肟酯化合物亦較佳為下述通式(B)所表示的化合物。 In the present invention, the oxime ester compound as a photopolymerization initiator is also preferably represented by the following formula (B) from the viewpoints of sensitivity, stability over time, and coloration upon post-heating. Compound.

通式(B)中，R22表示一價取代基。A22表示二價連結基，Ar表示芳基。n為0~5的整數。X22表示一價取代基，在n為2~4的整數的情況下存在多個的X22可相同亦可不同。 In the formula (B), R 22 represents a monovalent substituent. A 22 represents a divalent linking group, and Ar represents an aryl group. n is an integer from 0 to 5. X 22 represents a monovalent substituent, and in the case where n is an integer of 2 to 4, a plurality of X 22 may be the same or different.

上述R22所表示的一價取代基較佳為以下所示的一價非金屬原子團。 The monovalent substituent represented by the above R 22 is preferably a monovalent non-metal atom group shown below.

R22所表示的一價非金屬原子團可列舉：可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烷基磺醯基、可具有取代基的芳基磺醯基、可具有取代基的醯基、可具有取代基的雜環基等。 The monovalent non-metal atom group represented by R 22 may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent A mercapto group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

可具有取代基的烷基較佳為碳數1~30的烷基，例如可列舉：甲基、乙基、丙基、丁基、己基環戊基、環己基、三氟甲基等。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexylcyclopentyl group, a cyclohexyl group, and a trifluoromethyl group.

可具有取代基的芳基較佳為碳數6~30的芳基，例如可 列舉：苯基、聯苯基、1-萘基、2-萘基等。 The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, for example, Listed: phenyl, biphenyl, 1-naphthyl, 2-naphthyl and the like.

可具有取代基的烷基磺醯基較佳為碳數1~20的烷基磺醯基，例如可列舉：甲基磺醯基、乙基磺醯基等。 The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.

可具有取代基的芳基磺醯基較佳為碳數6~30的芳基磺醯基，例如可列舉：苯基磺醯基、1-萘基磺醯基等。 The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.

可具有取代基的醯基較佳為碳數2~20的醯基，例如可列舉：乙醯基、丙醯基、丁醯基、三氟甲基羰基、戊醯基、苯甲醯基、1-萘甲醯基、2-萘甲醯基、4-甲基硫烷基苯甲醯基、4-苯基硫烷基苯甲醯基、4-二甲基胺基苯甲醯基、4-二乙基胺基苯甲醯基、2-氯苯甲醯基、2-甲基苯甲醯基、2-甲氧基苯甲醯基、2-丁氧基苯甲醯基、3-氯苯甲醯基、3-三氟甲基苯甲醯基、3-氰基苯甲醯基、3-硝基苯甲醯基、4-氟苯甲醯基、4-氰基苯甲醯基、4-甲氧基苯甲醯基等。 The fluorenyl group which may have a substituent is preferably a fluorenyl group having 2 to 20 carbon atoms, and examples thereof include an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, a trifluoromethylcarbonyl group, a amyl group, a benzamidine group, and a group. Naphthylmethyl, 2-naphthylmethyl, 4-methylsulfanylbenzylidene, 4-phenylsulfanylbenzylidene, 4-dimethylaminobenzimidyl, 4- Diethylaminobenzimidyl, 2-chlorobenzhydryl, 2-methylbenzhydryl, 2-methoxybenzimidyl, 2-butoxybenzylidene, 3-chloro Benzopyridyl, 3-trifluoromethylbenzhydryl, 3-cyanobenzylidene, 3-nitrobenzhydryl, 4-fluorobenzhydryl, 4-cyanobenzylidene , 4-methoxybenzhydryl and the like.

可具有取代基的雜環基較佳為包含氮原子、氧原子、硫原子、磷原子的芳香族或者脂肪族的雜環。例如可列舉噻吩基、呋喃基、哌喃基等。 The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. For example, a thienyl group, a furyl group, a piperidyl group, etc. are mentioned.

就高感度化的方面而言，上述R22更佳為未經取代的或者具有取代基的醯基，具體而言較佳為未經取代的或者具有取代基的乙醯基、丙醯基、苯甲醯基、甲苯甲醯基。 In terms of high sensitivity, the above R 22 is more preferably an unsubstituted or substituted fluorenyl group, and particularly preferably an unsubstituted or substituted ethyl fluorenyl group, a propyl fluorenyl group, Benzopyridinyl, toluylcarbenyl.

上述取代基例如可列舉下述結構式所表示的基團，其中，較佳為(d-1)、(d-4)及(d-5)的任一者。 The substituent represented by the following structural formula is, for example, any of (d-1), (d-4) and (d-5).

上述A22所表示的二價連結基可列舉：可具有取代基的碳數1~12的伸烷基、可具有取代基的伸環己基、可具有取代基的伸炔基。 Examples of the divalent linking group represented by the above A 22 include an alkylene group having 1 to 12 carbon atoms which may have a substituent, a cyclohexylene group which may have a substituent, and an alkynyl group which may have a substituent.

可導入至該些基團中的取代基例如可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子，甲氧基、乙氧基、第三丁氧基等烷氧基，苯氧基、對甲苯氧基等芳氧基，甲氧基羰基、丁氧基羰基、苯氧基羰基等烷氧基羰基等。 Examples of the substituent which can be introduced into the group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group, and a phenoxy group. An aryloxy group such as a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; and the like.

其中，就提高感度、抑制隨加熱時間經過而引起的著色的方面而言，上述A22較佳為未經取代的伸烷基、經烷基(例如：甲基、乙基、第三丁基、十二烷基)取代的伸烷基、經烯基(例如：乙烯基、烯丙基)取代的伸烷基、經芳基(例如：苯基、對甲苯基、二甲苯基、異丙苯基、萘基、蒽基、菲基、苯乙烯基)取代的伸烷基。 Wherein, in terms of improving the sensitivity and suppressing the coloring caused by the passage of the heating time, the above A 22 is preferably an unsubstituted alkylene group, an alkyl group (for example, a methyl group, an ethyl group, a third butyl group). , dodecyl) substituted alkylene, alkylene substituted by alkenyl (eg vinyl, allyl), aryl (eg phenyl, p-tolyl, xylyl, isopropyl) Phenyl, naphthyl, anthracenyl, phenanthryl, styryl) substituted alkylene.

上述Ar所表示的芳基較佳為碳數6~30的芳基，另外，可具有取代基。 The aryl group represented by the above Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.

具體而言，Ar可列舉：苯基、聯苯基、1-萘基、2-萘基、聯三苯基、聯四苯基、鄰甲苯基、間甲苯基、及對甲苯基、二甲苯基、鄰異丙苯基、間異丙苯基、及對異丙苯基、均三甲苯基(mesityl group)等。其中，就提高感度、抑制隨加熱時間經過引起的著色的方面而言，較佳為經取代或未經取代的苯基。 Specifically, Ar may be exemplified by phenyl, biphenyl, 1-naphthyl, 2-naphthyl, triphenyl, biphenyl, o-tolyl, m-tolyl, p-tolyl, xylene Base, o-isopropylphenyl, m-isopropylphenyl, and p-cumyl, mesityl group, and the like. Among them, a substituted or unsubstituted phenyl group is preferred in terms of improving the sensitivity and suppressing the coloring caused by the passage of the heating time.

在上述苯基具有取代基的情況下，該取代基例如可列舉：氟原子、氯原子、溴原子、碘原子等鹵素原子，甲氧基、乙氧基、第三丁氧基等烷氧基，苯氧基、對甲苯氧基等芳氧基，甲氧基羰基、丁氧基羰基、苯氧基羰基等烷氧基羰基，乙醯氧基、丙醯氧基、苯甲醯氧基等醯氧基，乙醯基、苯甲醯基、異丁醯基、丙烯醯基、甲基丙烯醯基、甲氧草醯基(methoxalyl)等醯基，甲基胺基、環己基胺基等烷基胺基，二甲基胺基、二乙基胺基、嗎啉基、哌啶基等二烷基胺基，苯基胺基，甲基、乙基、第三丁基、十二烷基等烷基，羥基、羧基等。 When the phenyl group has a substituent, the substituent may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or an alkoxy group such as a methoxy group, an ethoxy group or a third butoxy group. An aryloxy group such as a phenoxy group or a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, a butoxycarbonyl group or a phenoxycarbonyl group; an ethoxy group, a propenyloxy group, a benzamidine group or the like. An alkyl group such as an anthracene group, an ethyl fluorenyl group, a benzamidine group, an isobutyl group, an acryl fluorenyl group, a methacryl fluorenyl group, a methoxalyl group, a methyl group or a cyclohexylamino group. a dialkylamino group such as an amine group, a dimethylamino group, a diethylamino group, a morpholinyl group or a piperidinyl group, a phenylamino group, a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, etc. Alkyl group, hydroxyl group, carboxyl group, and the like.

通式(B)中，若由上述Ar與鄰接的S形成的「SAr」的結構為以下所示的結構，則就感度的方面而言較佳。 In the general formula (B), when the structure of "SAr" formed of the above Ar and the adjacent S is as follows, it is preferable in terms of sensitivity.

上述X22所表示的一價取代基可列舉：可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烯基、可具有取代基的炔基、可具有取代基的烷氧基、可具有取代基的芳氧基、可具有取代基的烷基硫基氧基、可具有取代基的芳基硫基氧基、鹵素原子等。 The monovalent substituent represented by the above X 22 may, for example, be an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, and a substituent which may have a substituent An alkoxy group, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, an arylthiooxy group which may have a substituent, a halogen atom, etc.

可具有取代基的烷基較佳為碳數1~30的烷基，例如可 列舉：甲基、乙基、丙基、丁基、己基、環戊基、環己基、三氟甲基、2-乙基己基、苯甲醯甲基等。 The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, Listed are: methyl, ethyl, propyl, butyl, hexyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, benzamidine methyl and the like.

可具有取代基的芳基較佳為碳數6~30的芳基，例如有：苯基、聯苯基、1-萘基、2-萘基、聯三苯基、聯四苯基、鄰甲苯基、間甲苯基、及對甲苯基、二甲苯基等。 The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a tetraphenyl group, and an adjacent group. Tolyl, m-tolyl, p-tolyl, xylyl and the like.

可具有取代基的烯基較佳為碳數2~10的烯基，例如可列舉：乙烯基、烯丙基、苯乙烯基等。 The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

可具有取代基的炔基較佳為碳數2~10的炔基，例如可列舉：乙炔基、丙炔基、炔丙基等。 The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

可具有取代基的烷氧基較佳為碳數1~30的烷氧基，例如可列舉：甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、苄氧基等。 The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a benzyloxy group, and the like. .

可具有取代基的芳氧基較佳為碳數6~30的芳氧基，例如可列舉：苯氧基、1-萘氧基、2-萘氧基、2-氯苯氧基、2-甲基苯氧基、2-甲氧基苯氧基等。 The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, and examples thereof include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenoxy group, and a 2- Methylphenoxy, 2-methoxyphenoxy and the like.

可具有取代基的烷基硫基氧基較佳為碳數1~30的硫基烷氧基，例如可列舉：甲基硫基氧基、乙基硫基氧基、丙基硫基氧基、異丙基硫基氧基、丁基硫基氧基、異丁基硫基氧基、第二丁基硫基氧基、第三丁基硫基氧基、戊基硫基氧基、異戊基硫基氧基、己基硫基氧基、庚基硫基氧基、辛基硫基氧基、2-乙基己基硫基氧基、癸基硫基氧基、十二烷基硫基氧基、十八烷基硫基 氧基、苄基硫基氧基等。 The alkylthiooxy group which may have a substituent is preferably a thioalkyloxy group having 1 to 30 carbon atoms, and examples thereof include a methylthiooxy group, an ethylthiooxy group, and a propylthiooxy group. , isopropylthiooxy, butylthiooxy, isobutylthiooxy, second butylthiooxy, tert-butylthiooxy, pentylthiooxy, iso Pentylthiooxy, hexylthiooxy, heptylthiooxy, octylthiooxy, 2-ethylhexylthiooxy, decylthiooxy, dodecylthio Oxyl, octadecylthio An oxy group, a benzylthiooxy group or the like.

可具有取代基的芳基硫基氧基較佳為碳數6~30的芳基硫基氧基，例如有：苯基硫基氧基、1-萘基硫基氧基、2-萘基硫基氧基、2-氯苯基硫基氧基、2-甲基苯基硫基氧基、2-甲氧基苯基硫基氧基、2-丁氧基苯基硫基氧基、3-氯苯基硫基氧基、3-三氟甲基苯基硫基氧基、3-氰基苯基硫基氧基、3-硝基苯基硫基氧基、4-氟苯基硫基氧基、4-氰基苯基硫基氧基、4-甲氧基苯基硫基氧基、4-二甲基胺基苯基硫基氧基、4-甲基硫烷基苯基硫基氧基、4-苯基硫烷基苯基硫基氧基等。 The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, and examples thereof include a phenylthiooxy group, a 1-naphthylthiooxy group, and a 2-naphthyl group. Thiooxy, 2-chlorophenylthiooxy, 2-methylphenylthiooxy, 2-methoxyphenylthiooxy, 2-butoxyphenylthiooxy, 3-chlorophenylthiooxy, 3-trifluoromethylphenylthiooxy, 3-cyanophenylthiooxy, 3-nitrophenylthiooxy, 4-fluorophenyl Thiooxy, 4-cyanophenylthiooxy, 4-methoxyphenylthiooxy, 4-dimethylaminophenylthiooxy, 4-methylsulfanylbenzene Alkylthiooxy, 4-phenylsulfanylphenylthiooxy, and the like.

鹵素原子有氟原子、氯原子、溴原子、碘原子等。 The halogen atom has a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like.

可具有取代基的鹵化烷基可列舉：單氟甲基、二氟甲基、三氟甲基、二氯甲基、三氯甲基、單溴甲基、二溴甲基、三溴甲基等。 The halogenated alkyl group which may have a substituent may, for example, be a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group or a tribromomethyl group. Wait.

N上可具有取代基的醯胺基可列舉：N,N-二甲基醯胺基、N,N-二乙基醯胺基等。 Examples of the guanamine group which may have a substituent on N include an N,N-dimethylammonium group, an N,N-diethylguanamine group, and the like.

該些基團中，就溶劑溶解性及長波長區域的吸收效率提高的方面而言，X22較佳為：可具有取代基的烷基、可具有取代基的芳基、可具有取代基的烯基、可具有取代基的炔基、可具有取代基的烷氧基、可具有取代基的芳氧基、可具有取代基的烷基硫基氧基、可具有取代基的芳基硫基氧基、可具有取代基的鹵化烷基、可具有取代基的胺基、或者N上可具有取代基的醯胺基，其 中更佳為可具有取代基的烷基。 Among these groups, X 22 is preferably an alkyl group which may have a substituent, an aryl group which may have a substituent, may have a substituent, in terms of improvement in solvent solubility and absorption efficiency in a long wavelength region. Alkenyl group, alkynyl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylthiooxy group which may have a substituent, arylthio group which may have a substituent An oxy group, a halogenated alkyl group which may have a substituent, an amine group which may have a substituent, or a guanamine group which may have a substituent on N, and more preferably an alkyl group which may have a substituent.

另外，通式(B)中的n表示0~5的整數，就合成的容易度的觀點而言，較佳為0~3的整數，更佳為0~2的整數。 Further, n in the general formula (B) represents an integer of 0 to 5, and is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2, from the viewpoint of easiness of synthesis.

通式(B)中，在X22存在多個的情況下，多個X22可相同，亦可不同。 In the general formula (B), when a plurality of X 22 are present, the plurality of X 22 may be the same or different.

以下表示上述通式(B)所表示的肟光聚合起始劑的具體例。 Specific examples of the photopolymerization initiator represented by the above formula (B) are shown below.

本發明中使用的通式(B)所表示的化合物是在250 nm~500 nm的波長區域具有吸收波長的化合物。更佳為可列舉在300 nm~380 nm的波長區域具有吸收波長的化合物。特佳為308 nm及355 nm的吸光度高的化合物。 The compound represented by the formula (B) used in the present invention is a compound having an absorption wavelength in a wavelength region of from 250 nm to 500 nm. More preferably, it is a compound having an absorption wavelength in a wavelength range of 300 nm to 380 nm. Particularly preferred are compounds with high absorbance at 308 nm and 355 nm.

具體而言，有機鹵化化合物的例子可列舉：若林等人的「日本化學會通報(Bulletin of the Chemical Society of Japan，Bull Chem.Soc.Japan)」第42卷第2924頁(1969)、美國專利第3,905,815號說明書、日本專利特公昭46-4605號公報、日本專利特開昭48-36281號公報、日本專利特開昭55-32070號公報、日本專利特開昭60-239736號公報、日本專利特開昭61-169835號公報、日本專利特開昭61-169837號公報、日本專利特開昭62-58241號公報、日本專利特開昭62-212401號公報、日本專利特開昭63-70243號公報、日本專利特開昭63-298339號公報、M.P.Hutt「雜環化學雜誌(Journal of Heterocyclic Chemistry)」1(No.3),(1970)等中記載的化合物；尤其可列舉三鹵甲基所取代的噁唑化合物、均三嗪化合物。 Specific examples of the organic halogenated compound include "Bulletin of the Chemical Society of Japan, Bull Chem. Soc. Japan", Vol. 42, pp. 2924 (1969), and U.S. Patent. Japanese Patent No. 3,905,815, Japanese Patent Publication No. Sho 46-4605, Japanese Patent Laid-Open No. SHO-48-36281, Japanese Patent Laid-Open No. Sho 55-32070, Japanese Patent Laid-Open Publication No. SHO-60-239736, Japanese Patent JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, and JP-A-63-70243 Japanese Laid-Open Patent Publication No. SHO 63-298339, MP Hutt, "Journal of Heterocyclic Chemistry" 1 (No. 3), (1970), etc.; An oxazole compound or a s-triazine compound substituted with a group.

六芳基聯咪唑化合物的例子例如可列舉日本專利特公平6-29285號公報、美國專利第3,479,185號、美國專利第4,311,783號、美國專利第4,622,286號等的各說明書中記載的各種化合物，具體而言為：2,2'-雙(鄰氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰溴苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(o,p-二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰氯苯基)-4,4',5,5'-四(間甲氧基苯基)聯咪唑、2,2'-雙(o,o'-二氯苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰硝基苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰甲基苯基)-4,4',5,5'-四苯基聯咪唑、2,2'-雙(鄰三氟苯基)-4,4',5,5'-四苯基聯咪唑等。 Examples of the hexaarylbiimidazole compound include, for example, various compounds described in the respective specifications, such as Japanese Patent Publication No. Hei. 6-29285, U.S. Patent No. 3,479,185, U.S. Patent No. 4,311,783, and U.S. Patent No. 4,622,286. It is: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-double (o-chlorophenyl)-4,4',5,5'-tetrakis(m-methoxyphenyl)biimidazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4 ',5,5'-Tetraphenylbiimidazole, 2,2'-bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis ( o-Methylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenyl Biimidazole and the like.

光聚合起始劑可使用1種或將2種以上組合使用。在使用2種以上的光聚合起始劑的情況下，可使用多種由通式(B)所表示的化合物，亦可使用多種由通式(II)所表示的化合物。另外，亦可分別使用通式(II)及通式(III)所表示的化合物中的至少1種。另外，亦可使用通式(II)及通式(III)所表示的化合物分別至少1種、以及通式(II)及通式(III)所表示的化合物以外的肟化合物或者肟化合物以外的光聚合起始劑。另外，亦可併用增感劑。 The photopolymerization initiator may be used alone or in combination of two or more. When two or more kinds of photopolymerization initiators are used, a plurality of compounds represented by the formula (B) can be used, and a plurality of compounds represented by the formula (II) can also be used. Further, at least one of the compounds represented by the general formula (II) and the general formula (III) may be used. In addition, at least one of the compounds represented by the general formula (II) and the general formula (III), and other than the hydrazine compound or the hydrazine compound other than the compound represented by the general formula (II) and the general formula (III). Photopolymerization initiator. In addition, a sensitizer may also be used in combination.

相對於著色感光性組成物中的總固體成分，光聚合起始劑的總含量較佳為0.1質量%~20質量%，更佳為0.5質量%~10質量%，最佳為1質量%~10質量%。若為該範圍內，則曝光時的感度高，另外色特性亦良好。 The total content of the photopolymerization initiator is preferably from 0.1% by mass to 20% by mass, more preferably from 0.5% by mass to 10% by mass, most preferably 1% by mass based on the total solid content of the coloring photosensitive composition. 10% by mass. If it is in this range, the sensitivity at the time of exposure is high, and the color characteristics are also favorable.

〈(E)鹼可溶性黏合劑〉 <(E) Alkali Soluble Binder>

本發明的著色感光性組成物中，為了提高被膜形成性，另外，就圖案形成性的觀點而言，較佳為使用鹼可溶性黏合劑。 In the colored photosensitive composition of the present invention, in order to improve film formability, an alkali-soluble binder is preferably used from the viewpoint of pattern formability.

鹼可溶性黏合劑除了具有鹼可溶性以外，並無特別限定，較佳為可根據耐熱性、顯影性、獲取性等觀點來選擇。 The alkali-soluble binder is not particularly limited as long as it has alkali solubility, and is preferably selected from the viewpoints of heat resistance, developability, and availability.

鹼可溶性黏合劑較佳為線狀有機高分子聚合物，且為可溶於有機溶劑中，能夠以弱鹼水溶液進行顯影的聚合物。此種線狀有機高分子聚合物可列舉側鏈上具有羧酸的聚合物，例如：如日本專利特開昭59-44615號、日本專利特公昭54-34327號、日本 專利特公昭58-12577號、日本專利特公昭54-25957號、日本專利特開昭59-53836號、日本專利特開昭59-71048號的各公報中記載的甲基丙烯酸共聚物、丙烯酸共聚物、亞甲基丁二酸共聚物、丁烯酸共聚物、順丁烯二酸共聚物、部分酯化順丁烯二酸共聚物等，同樣可使用在側鏈上具有羧酸的酸性纖維素衍生物。 The alkali-soluble binder is preferably a linear organic high molecular polymer, and is a polymer which is soluble in an organic solvent and can be developed with a weak aqueous alkali solution. Examples of such a linear organic high molecular polymer include a polymer having a carboxylic acid in a side chain, for example, Japanese Patent Laid-Open No. Sho 59-44615, Japanese Patent Publication No. Sho 54-34327, and Japan The methacrylic acid copolymer and the acrylic acid copolymer described in each of the publications of Japanese Patent Laid-Open Publication No. Sho 59-57, s. , methylene succinic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., acid fiber having a carboxylic acid in a side chain can also be used. A derivative.

除了上述聚合物以外，鹼可溶性黏合劑亦可使用：在具有羥基的聚合物上加成有酸酐的聚合物等，或聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、聚((甲基)丙烯酸2-羥基乙酯)、聚乙烯基吡咯啶酮或聚環氧乙烷、聚乙烯醇等。另外，線狀有機高分子聚合物可為將具有親水性的單體進行共聚合而成的聚合物。其例子可列舉：(甲基)丙烯酸烷氧基烷基酯、(甲基)丙烯酸羥基烷基酯、甘油(甲基)丙烯酸酯、(甲基)丙烯醯胺、N-羥甲基丙烯醯胺、二級或三級烷基丙烯醯胺、(甲基)丙烯酸二烷基胺基烷基酯、嗎啉(甲基)丙烯酸酯、N-乙烯基吡咯啶酮、N-乙烯基己內醯胺、乙烯基咪唑、乙烯基***、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、分支或直鏈的(甲基)丙烯酸丙酯、分支或直鏈的(甲基)丙烯酸丁酯、或者(甲基)丙烯酸苯氧基羥基丙酯等。此外，具有親水性的單體亦可使用包含四氫糠基、磷酸基、磷酸酯基、四級銨鹽基、伸乙基氧基鏈、伸丙基氧基鏈、磺酸基及源自其鹽的基團、嗎啉基乙基等而形成的單體等。 In addition to the above polymers, an alkali-soluble binder may be used: a polymer having an acid anhydride added to a polymer having a hydroxyl group, or a polyhydroxystyrene resin, a polyoxyalkylene resin, or a poly(methyl group). ) 2-hydroxyethyl acrylate), polyvinylpyrrolidone or polyethylene oxide, polyvinyl alcohol, and the like. Further, the linear organic high molecular polymer may be a polymer obtained by copolymerizing a monomer having hydrophilicity. Examples thereof include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth) acrylate, (meth) acrylamide, and N-methylol propylene oxime. Amine, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone, N-vinyl hexene Indoleamine, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear (methyl) Butyl acrylate or phenoxy hydroxypropyl (meth)acrylate. Further, the hydrophilic monomer may also contain a tetrahydroindenyl group, a phosphoric acid group, a phosphate group, a quaternary ammonium salt group, an extended ethyloxy chain, a propyloxy chain, a sulfonic acid group, and a source thereof. a monomer formed by a salt group, a morpholinylethyl group or the like.

另外，為了提高交聯效率，鹼可溶性黏合劑可在側鏈上 具有聚合性基，例如亦可使用側鏈上含有烯丙基、(甲基)丙烯醯基、烯丙基氧基烷基等的聚合物等。上述含有聚合性基的聚合物的例子可列舉：Dianal NR系列(三菱麗陽(Mitsubishi Rayon)股份有限公司製造)、Photomer 6173(含COOH的聚胺基甲酸酯丙烯酸低聚物(polyurethane acrylic oligomer，鑽石三葉草股份有限公司(Diamond Shamrock Co.Ltd.,)製造))，Viscoat R-264、KS Resist 106(均由大阪有機化學工業股份有限公司製造)，Cyclomer P系列、Placcel CF200系列(均由大賽璐化學工業(Daicel Chemical industries)股份有限公司製造)，Ebecryl 3800(大賽璐UCB(Daicel-UCB)股份有限公司製造)等。另外，為了提高硬化皮膜的強度，亦可使用醇可溶性尼龍或2,2-雙-(4-羥基苯基)-丙烷與表氯醇的聚醚等。 In addition, in order to improve the crosslinking efficiency, the alkali-soluble binder can be on the side chain. The polymerizable group may, for example, be a polymer containing an allyl group, a (meth) acryl fluorenyl group, an allyloxyalkyl group or the like in a side chain. Examples of the polymerizable group-containing polymer include a Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.) and Photomer 6173 (a COOH-containing polyurethane urethane oligomer). , Diamond Shamrock Co., Ltd.), Viscoat R-264, KS Resist 106 (both manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Placcel CF200 series (all by It is manufactured by Daicel Chemical Industries Co., Ltd., Ebecryl 3800 (manufactured by Daicel-UCB Co., Ltd.). Further, in order to increase the strength of the hardened film, an alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epichlorohydrin may be used.

該些各種鹼可溶性黏合劑中，就耐熱性的觀點而言，較佳為聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯醯基/丙烯醯胺共聚物樹脂，就顯影性控制的觀點而言，較佳為丙烯酸系樹脂、丙烯醯胺系樹脂、丙烯醯基/丙烯醯胺共聚物樹脂。 Among these various alkali-soluble binders, from the viewpoint of heat resistance, a polyhydroxystyrene resin, a polyoxyalkylene resin, an acrylic resin, an acrylamide resin, and an acrylonitrile/acrylonitrile are preferable. The amine copolymer resin is preferably an acrylic resin, an acrylamide resin, or an acrylonitrile/acrylamide copolymer resin from the viewpoint of developability control.

上述丙烯酸系樹脂較佳為由選自由(甲基)丙烯酸苄酯、(甲基)丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基)丙烯醯胺等所組成組群中的單體形成的共聚物，或上述Photomer 6173、KS Resist-106、Cyclomer P系列等。 The acrylic resin is preferably formed of a monomer selected from the group consisting of benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, and the like. Copolymer, or the above Photomer 6173, KS Resist-106, Cyclomer P series, and the like.

就顯影性、液黏度等觀點而言，鹼可溶性黏合劑較佳為重量平均分子量(以凝膠滲透層析(gel permeation chromatography，GPC)法測定的聚苯乙烯換算值)為1000~2×105的聚合物，更佳為2000~1×105的聚合物，特佳為5000~5×104的聚合物。可單獨使用，亦可併用2種以上。 The alkali-soluble binder preferably has a weight average molecular weight (polystyrene-converted value measured by a gel permeation chromatography (GPC) method) of 1000 to 2 × 10 in terms of developability, liquid viscosity, and the like. The polymer of 5 is more preferably a polymer of 2000 to 1 × 10 5 , particularly preferably a polymer of 5000 to 5 × 10 4 . They may be used alone or in combination of two or more.

〈其他成分〉 <Other ingredients>

本發明的著色感光性組成物中，進而視需要，只要不損及本發明的效果，則可含有公知的添加劑，例如：多官能硫醇化合物、鏈轉移劑、聚合抑制劑、有機溶劑、界面活性劑、密接改良劑、交聯劑、顯影促進劑、以及其他添加劑。 The colored photosensitive composition of the present invention may further contain a known additive as long as the effect of the present invention is not impaired, for example, a polyfunctional thiol compound, a chain transfer agent, a polymerization inhibitor, an organic solvent, or an interface. Active agent, adhesion improver, crosslinking agent, development accelerator, and other additives.

以下對該些成分進行說明。 The components are described below.

(多官能硫醇化合物) (multifunctional thiol compound)

本發明的著色感光性組成物可含有多官能硫醇化合物。 The colored photosensitive composition of the present invention may contain a polyfunctional thiol compound.

本發明的著色感光性組成物藉由包含多官能硫醇化合物，而提高感度，抑制由染料等有色材料引起的離子溶出等，當在液晶顯示裝置的彩色濾光片製作中使用本發明的著色感光性組成物時，可防止串擾(crosstalk)等畫質的劣化，可進行鮮明的高畫質的顯示。 The colored photosensitive composition of the present invention contains a polyfunctional thiol compound to improve sensitivity, suppress ion elution by a colored material such as a dye, and the like, and uses the coloring of the present invention in color filter production of a liquid crystal display device. In the case of a photosensitive composition, deterioration in image quality such as crosstalk can be prevented, and a clear high-quality display can be performed.

本發明中所謂「多官能硫醇化合物」，是指分子內具有2個以上硫醇基的化合物。上述多官能硫醇化合物較佳為分子量為100以上的低分子化合物，具體而言，分子量較佳為100~1500， 尤佳為150~1000。上述多官能硫醇化合物較佳為在分子內具有2個~10個的硫醇基，尤佳為具有2個~6個的硫醇基。另外，該些化合物較佳為設為在上述自由基聚合性單體聚合時輔助使用的系統。具體而言，較佳為使多官能硫醇化合物的添加量相對於組成物的總固體成分而為1質量%~20質量%，或設為較同時含有的上述自由基聚合性單體的添加量少的添加量。 The "polyfunctional thiol compound" in the present invention means a compound having two or more thiol groups in the molecule. The polyfunctional thiol compound is preferably a low molecular compound having a molecular weight of 100 or more, and specifically, the molecular weight is preferably from 100 to 1,500. Especially good is 150~1000. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, and more preferably has 2 to 6 thiol groups. Further, these compounds are preferably used as a system for assisting use in the polymerization of the above-mentioned radical polymerizable monomer. Specifically, the amount of the polyfunctional thiol compound to be added is preferably 1% by mass to 20% by mass based on the total solid content of the composition, or the addition of the above-mentioned radical polymerizable monomer is preferably contained. A small amount of addition.

本發明中可使用的多官能硫醇化合物的具體例例如可列舉以下化合物作為較佳的多官能硫醇化合物：三羥甲基丙烷三(3-巰基丙酸酯)、季戊四醇四(3-巰基丙酸酯)、四乙二醇雙(3-巰基丙酸酯)、二季戊四醇六(3-巰基丙酸酯)、季戊四醇四(硫基乙醇酸酯)、季戊四醇四(3-巰基丁酸酯)、丁二醇雙(3-巰基丁酸酯)、1,4-雙(3-巰基丁氧基)丁烷、1,3,5-三(3-巰基丁氧基乙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮等。 Specific examples of the polyfunctional thiol compound which can be used in the present invention include, for example, the following compounds as preferred polyfunctional thiol compounds: trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercapto) Propionate), tetraethylene glycol bis(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), pentaerythritol tetrakis(thioglycolate), pentaerythritol tetrakis(3-mercaptobutyrate) ), butanediol bis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1 , 3,5-triazine-2,4,6(1H,3H,5H)-trione and the like.

相對於著色感光性組成物中的總固體成分，多官能硫醇化合物的含量較佳為0.01質量%~20質量%，尤佳為0.1質量%~10質量%。若多官能硫醇化合物的含量在該範圍內，則著色感光性組成物的感度良好，保存穩定性良好，所得彩色濾光片中的畫素的密接性良好且無圖案缺陷，可提供在用於液晶顯示裝置的情況下電氣特性良好的著色感光性組成物。 The content of the polyfunctional thiol compound is preferably from 0.01% by mass to 20% by mass, particularly preferably from 0.1% by mass to 10% by mass, based on the total solid content of the coloring photosensitive composition. When the content of the polyfunctional thiol compound is within this range, the sensitivity of the colored photosensitive composition is good, the storage stability is good, and the adhesion of the pixels in the obtained color filter is good and there is no pattern defect, and it can be provided for use. A colored photosensitive composition having excellent electrical characteristics in the case of a liquid crystal display device.

(增感劑) (sensitizer)

本發明的著色感光性組成物中亦可添加增感劑。本發明 中使用的典型增感劑可列舉Crivello[J.V.Crivello，聚合物科學進展(Advances in Polymer Science，Adv.in Polymer Sci)第62卷第1期(1984)]中揭示的增感劑，具體而言可列舉：芘(pyrene)、苝(perylene)、吖啶、噻噸酮(thioxanthone)、2-氯噻噸酮(2-chlorothioxanthone)、苯并黃素(benzoflavine)、N-乙烯基咔唑、9,10-二丁氧基蒽、蒽醌、二苯甲酮、香豆素、香豆素酮(ketocoumarin)、菲(phenanthrene)、樟腦醌(camphorquinone)、吩噻嗪衍生物等。相對於光聚合起始劑，增感劑較佳為以50質量%~200質量%的比例添加。 A sensitizer may be added to the colored photosensitive composition of the present invention. this invention Typical sensitizers used in the sensitizers disclosed in Crivello [JVCrivello, Advances in Polymer Science, Adv. in Polymer Sci, Vol. 62, No. 1 (1984)], in particular Usa: pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10-dibutoxy oxime, hydrazine, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivative, and the like. The sensitizer is preferably added in a proportion of 50% by mass to 200% by mass based on the photopolymerization initiator.

(鏈轉移劑) (chain transfer agent)

本發明的著色感光性組成物中亦可添加鏈轉移劑。本發明中使用的鏈轉移劑例如可列舉：N,N-二甲基胺基苯甲酸乙酯等N,N-二烷基胺基苯甲酸烷基酯、2-巰基苯并噻唑、2-巰基苯并噁唑、2-巰基苯并咪唑、N-苯基巰基苯并咪唑等具有雜環的巰基化合物等。 A chain transfer agent may also be added to the colored photosensitive composition of the present invention. The chain transfer agent used in the present invention may, for example, be an N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, or 2- A mercapto compound having a heterocyclic ring such as mercaptobenzoxazole, 2-mercaptobenzimidazole or N-phenylmercaptobenzimidazole.

鏈轉移劑可單獨使用1種，亦可併用2種以上。 The chain transfer agent may be used singly or in combination of two or more.

就減少感度不均的觀點而言，相對於本發明的著色感光性組成物的總固體成分，鏈轉移劑的添加量較佳為0.01質量%~15質量%的範圍，更佳為0.1質量%~10質量%，特佳為0.5質量%~5質量%。 The amount of the chain transfer agent added is preferably in the range of 0.01% by mass to 15% by mass, more preferably 0.1% by mass, based on the total solid content of the coloring photosensitive composition of the present invention, from the viewpoint of reducing the sensitivity unevenness. ~10% by mass, particularly preferably 0.5% by mass to 5% by mass.

(聚合抑制劑) (polymerization inhibitor)

本發明的著色感光性組成物可含有聚合抑制劑。 The colored photosensitive composition of the present invention may contain a polymerization inhibitor.

所謂聚合抑制劑，是指發揮如下作用的物質：對藉由光或熱而於著色感光性組成物中產生的自由基等聚合起始種進行氫供與(或者氫授與)、能量供與(或者能量授與)、電子供與(或者電子授與)等，使聚合起始種失活，抑制不經意地開始的聚合。可使用日本專利特開2007-334322號公報的段落0154~0173中記載的聚合抑制劑等。 The term "polymerization inhibitor" refers to a substance that performs hydrogen supply (or hydrogen donation) and energy supply to a polymerization starting species such as a radical generated in a colored photosensitive composition by light or heat. (or energy imparting), electron donating (or electron donating), etc., inactivation of the polymerization starting species, and suppression of polymerization initiated inadvertently. A polymerization inhibitor or the like described in paragraphs 0154 to 0173 of JP-A-2007-334322 can be used.

該些物質中，聚合抑制劑較佳為可列舉對甲氧基苯酚。 Among these, the polymerization inhibitor is preferably p-methoxyphenol.

相對於聚合性化合物的總質量，本發明的著色感光性組成物中的聚合抑制劑的含量較佳為0.0001質量%~5質量%，更佳為0.001質量%~5質量%，特佳為0.001質量%~1質量%。 The content of the polymerization inhibitor in the coloring photosensitive composition of the present invention is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass, even more preferably 0.001, based on the total mass of the polymerizable compound. Mass %~1% by mass.

[(F)有機溶劑] [(F) organic solvent]

本發明的著色感光性組成物較佳為含有(F)有機溶劑。 The colored photosensitive composition of the present invention preferably contains (F) an organic solvent.

另外，本發明的分散組成物較佳為含有(F)有機溶劑。 Further, the dispersion composition of the present invention preferably contains (F) an organic solvent.

分散組成物所包含的有機溶劑與著色感光性組成物所包含的有機溶劑可為同種，亦可為不同種，分散組成物所包含的有機溶劑與著色感光性組成物所包含的有機溶劑可為1種，亦可為2種以上。 The organic solvent contained in the dispersion composition and the organic solvent contained in the colored photosensitive composition may be the same kind or different types, and the organic solvent contained in the dispersion composition and the organic solvent contained in the colored photosensitive composition may be One type may be used in two or more types.

(F)有機溶劑只要是可滿足所並存的各成分的溶解性或者製成著色感光性組成物時的塗佈性的溶劑，則基本上並無特別限制，特佳為考慮到固體成分的溶解性、塗佈性、安全性來選 擇。 (F) The organic solvent is not particularly limited as long as it is a solvent which satisfies the solubility of each component to be coherent or the coloring of the photosensitive composition, and is particularly preferably considered to dissolve the solid component. Sex, coating, safety Choose.

作為(F)有機溶劑，酯類例如可列舉：乙酸乙酯、乙酸-正丁酯、乙酸異丁酯、甲酸戊酯、乙酸異戊酯、乙酸異丁酯、丙酸丁酯、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳酸甲酯、乳酸乙酯、氧乙酸烷基酯類(例：氧乙酸甲酯、氧乙酸乙酯、氧乙酸丁酯(具體而言，可列舉：甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯等))、3-氧丙酸烷基酯類、2-氧丙酸烷基酯類、2-氧-2-甲基丙酸甲酯、2-氧-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯等另外，醚類例如可列舉：二乙二醇二甲醚、四氫呋喃、乙二醇單甲醚、乙二醇單***、甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、二乙二醇乙基甲醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等。 Examples of the (F) organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, and butyric acid. Propyl ester, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, Listed: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-oxopropionate, Alkyl 2-oxopropionate, methyl 2-oxo-2-methylpropanoate, ethyl 2-oxo-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate Ethylacetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc. Further, examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, and ethyl Glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol single Dibutyl ether, diethylene glycol ethyl methyl ether, C Glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate.

酮類例如可列舉：甲基乙基酮、環己酮、2-庚酮、3-庚酮等。 Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

芳香族烴類例如可適宜列舉甲苯、二甲苯等。 Examples of the aromatic hydrocarbons include toluene, xylene, and the like.

就上述各成分的溶解性、以及在包含鹼可溶性黏合劑的情況下的該鹼可溶性黏合劑的溶解性、塗佈面狀的改良等觀點而言，該些有機溶劑亦較佳為將2種以上混合。該情況下，特佳為 包含選自以下溶劑中的2種以上的混合溶液：3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙基溶纖劑乙酸酯、乳酸乙酯、二乙二醇二甲醚、二乙二醇乙基甲醚、乙酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇甲醚、及丙二醇甲醚乙酸酯。 The organic solvent is preferably two in terms of the solubility of each of the above components, the solubility of the alkali-soluble binder in the case of containing an alkali-soluble binder, and the improvement of the coating surface. Mix above. In this case, especially good Containing a mixed solution of two or more selected from the group consisting of methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, and diethyl Alcohol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbene Alcohol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

有機溶劑在著色感光性組成物中的含量較佳為著色感光性組成物中的總固體成分濃度成為10質量%~80質量%的量，更佳為成為15質量%~60質量%的量。 The content of the organic solvent in the coloring photosensitive composition is preferably such that the total solid content concentration in the colored photosensitive composition is from 10% by mass to 80% by mass, more preferably from 15% by mass to 60% by mass.

(界面活性劑) (surfactant)

本發明的著色感光性組成物可含有界面活性劑。 The colored photosensitive composition of the present invention may contain a surfactant.

界面活性劑可使用陰離子系界面活性劑、陽離子系界面活性劑、非離子系界面活性劑、或者兩性界面活性劑中的任一種，較佳的界面活性劑為非離子系界面活性劑。具體而言，可列舉日本專利特開2009-098616號公報的段落0058中記載的非離子系界面活性劑，其中較佳為氟系界面活性劑。 As the surfactant, any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant can be used, and a preferred surfactant is a nonionic surfactant. Specifically, a nonionic surfactant described in paragraph 0057 of JP-A-2009-098616 is preferable, and among them, a fluorine-based surfactant is preferable.

本發明中可使用的其他界面活性劑例如可列舉市售品，即：Megafac F142D、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F183、Megafac F479、Megafac F482、Megafac F554、Megafac F780、Megafac F781、Megafac F781-F、Megafac R30、Megafac R08、Megafac F-472SF、Megafac BL20、Megafac R-61、Megafac R-90(以上由DIC(股)製造)，Fluorad FC-135、Fluorad FC-170C、Fluorad FC-430、Fluorad FC-431、Novec FC-4430(以上由住友3M(股)製造)，Asahi Guard AG 7105、Asahi Guard AG 7000、Asahi Guard AG 950、Asahi Guard AG 7600、Surflon S-112、Surflon S-113、Surflon S-131、Surflon S-141、Surflon S-145、Surflon S-382、Surflon SC-101、Surflon SC-102、Surflon SC-103、Surflon SC-104、Surflon SC-105、Surflon SC-106(以上由旭硝子(股)製造)，Eftop EF351、Eftop EF 352、Eftop EF 801、Eftop EF 802(以上由三菱材料電子化成(股)製造)，Ftergent 250(尼歐斯(Neos)(股)製造)等。 Other surfactants which can be used in the present invention are, for example, commercially available products, namely, Megafac F142D, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac. F781, Megafac F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac R-90 (above manufactured by DIC), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431, Novec FC-4430 (above manufactured by Sumitomo 3M), Asahi Guard AG 7105, Asahi Guard AG 7000, Asahi Guard AG 950, Asahi Guard AG 7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (above manufactured by Asahi Glass Co., Ltd.), Eftop EF351, Eftop EF 352, Eftop EF 801, Eftop EF 802 (the above is manufactured by Mitsubishi Materials Electronics Co., Ltd.), Ftergent 250 (manufactured by Neos) and so on.

另外，界面活性劑可列舉如下共聚物作為較佳例子，該共聚物包含下述式(W)所表示的構成單元A及構成單元B，且以四氫呋喃作為溶劑，利用凝膠滲透層析法來測定的聚苯乙烯換算的重量平均分子量(Mw)為1,000以上10,000以下。 Further, the surfactant is preferably a copolymer comprising the structural unit A and the structural unit B represented by the following formula (W), and using tetrahydrofuran as a solvent, by gel permeation chromatography. The measured polystyrene-equivalent weight average molecular weight (Mw) is 1,000 or more and 10,000 or less.

(式(W)中，R1及R3分別獨立地表示氫原子或者甲基，R2表示碳數1以上4以下的直鏈伸烷基，R4表示氫原子或者 碳數1以上4以下的烷基，L表示碳數3以上6以下的伸烷基，p及q為表示聚合比的質量百分率，p表示10質量%以上80質量%以下的數值，q表示20質量%以上90質量%以下的數值，r表示1以上18以下的整數，n表示1以上10以下的整數。) (In the formula (W), R 1 and R 3 each independently represent a hydrogen atom or a methyl group, R 2 represents a linear alkylene group having 1 or more and 4 or less carbon atoms, and R 4 represents a hydrogen atom or a carbon number of 1 or more and 4 or less. The alkyl group, L represents an alkylene group having a carbon number of 3 or more and 6 or less, p and q are mass percentages indicating a polymerization ratio, p is a numerical value of 10% by mass or more and 80% by mass or less, and q is 20% by mass or more and 90% by mass or less. In the following numerical values, r represents an integer of 1 or more and 18 or less, and n represents an integer of 1 or more and 10 or less.)

上述L較佳為下述式(W-2)所表示的分支伸烷基。式(W-2)中的R5表示碳數1以上4以下的烷基，就相容性與對被塗佈面的潤濕性的方面而言，較佳為碳數1以上3以下的烷基，更佳為碳數2或3的烷基。 The above L is preferably a branched alkyl group represented by the following formula (W-2). R 5 in the formula (W-2) represents an alkyl group having 1 or more and 4 or less carbon atoms, and is preferably a carbon number of 1 or more and 3 or less in terms of compatibility and wettability to a surface to be coated. The alkyl group is more preferably an alkyl group having 2 or 3 carbon atoms.

式(W)中的p與q的和(p+q)較佳為p+q=100，即100質量%。 The sum (p+q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.

上述共聚物的重量平均分子量(Mw)更佳為1,500以上5,000以下。 The weight average molecular weight (Mw) of the above copolymer is more preferably 1,500 or more and 5,000 or less.

該些界面活性劑可單獨使用1種或者使用2種以上。 These surfactants may be used alone or in combination of two or more.

著色感光性組成物的總固體成分中，本發明的著色感光性組成物中的界面活性劑的添加量較佳為0.01質量%~2.0質量%，特佳為0.02質量%~1.0質量%。若為該範圍，則塗佈性及硬化膜的均勻性變得良好。 In the total solid content of the coloring photosensitive composition, the amount of the surfactant added to the coloring photosensitive composition of the present invention is preferably 0.01% by mass to 2.0% by mass, particularly preferably 0.02% by mass to 1.0% by mass. When it is this range, the coatability and the uniformity of a cured film become favorable.

(密接改良劑) (close contact improver)

本發明的著色感光性組成物可含有密接改良劑。 The colored photosensitive composition of the present invention may contain a adhesion improving agent.

密接改良劑是提高成為支持體的無機物與著色感光性組成物層的硬化膜的密接性的化合物，上述無機物為例如玻璃、矽、氧化矽、氮化矽等矽化合物，金、銅、鋁等。具體而言可列舉矽烷偶合劑等。作為密接改良劑的矽烷偶合劑是以界面的改質為目的，並無特別限定，可使用公知的化合物。 The adhesion improving agent is a compound which improves the adhesion between the inorganic substance serving as the support and the cured film of the colored photosensitive composition layer, and the inorganic substance is, for example, a bismuth compound such as glass, ruthenium, iridium oxide or tantalum nitride, gold, copper, aluminum, or the like. . Specific examples thereof include a decane coupling agent and the like. The decane coupling agent as the adhesion improving agent is not particularly limited as long as it is modified by the interface, and a known compound can be used.

矽烷偶合劑較佳為日本專利特開2009-98616號公報的段落0048中記載的矽烷偶合劑，其中更佳為γ-環氧丙氧基丙基三烷氧基矽烷或γ-甲基丙烯醯氧基丙基三烷氧基矽烷。該些化合物可單獨使用1種或併用2種以上。 The decane coupling agent is preferably a decane coupling agent described in paragraph 0048 of JP-A-2009-98616, wherein more preferably γ-glycidoxypropyltrialkoxydecane or γ-methylpropene oxime Oxypropyl propyl alkoxy decane. These compounds may be used alone or in combination of two or more.

相對於著色感光性組成物的總固體成分量，本發明的著色感光性組成物中的密接改良劑的含量較佳為0.1質量%~20質量%，更佳為0.2質量%~5質量%。 The content of the adhesion improving agent in the coloring photosensitive composition of the present invention is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.2% by mass to 5% by mass, based on the total solid content of the coloring photosensitive composition.

(交聯劑) (crosslinking agent)

本發明的著色感光性組成物中補充性地使用交聯劑，亦可更提高使著色感光性組成物硬化而成的著色層的硬度。 In the colored photosensitive composition of the present invention, a crosslinking agent is used in a complementary manner, and the hardness of the colored layer obtained by curing the colored photosensitive composition can be further improved.

交聯劑只要是可藉由交聯反應來進行膜硬化的交聯劑，則並無特別限定，例如可列舉：(a)環氧樹脂；(b)經選自羥甲基、烷氧基甲基及醯氧基甲基所組成組群中的至少1個取代基所取代的三聚氰胺化合物、胍胺(guanamine)化合物、甘脲 (glycoluril)化合物或者脲化合物；(c)經選自羥甲基、烷氧基甲基及醯氧基甲基所組成組群中的至少1個取代基所取代的苯酚化合物、萘酚化合物或者羥基蒽化合物。其中，較佳為多官能環氧樹脂。 The crosslinking agent is not particularly limited as long as it is a crosslinking agent which can be cured by a crosslinking reaction, and examples thereof include (a) an epoxy resin; and (b) a selected from a methylol group and an alkoxy group. a melamine compound, a guanamine compound, a glycoluril substituted with at least one substituent in a group consisting of a methyl group and a decyloxymethyl group a (glycoluril) compound or a urea compound; (c) a phenol compound or a naphthol compound substituted with at least one substituent selected from the group consisting of a methylol group, an alkoxymethyl group, and a decyloxymethyl group; Hydroxyl hydrazine compound. Among them, a polyfunctional epoxy resin is preferred.

關於交聯劑的具體例等的詳情，可參照日本專利特開2004-295116號公報的段落[0134]~[0147]的記載。 For details of specific examples of the crosslinking agent, etc., the descriptions of paragraphs [0134] to [0147] of JP-A-2004-295116 can be referred to.

(顯影促進劑) (development accelerator)

在促進對著色感光性組成物層進行曝光時的非曝光區域的鹼溶解性，實現著色感光性組成物的顯影性進一步提高的情況下，亦可添加顯影促進劑。顯影促進劑較佳為分子量為1000以下的低分子量有機羧酸化合物、分子量為1000以下的低分子量苯酚化合物。 When the alkali solubility in the non-exposed region when the coloring photosensitive composition layer is exposed is promoted, and the developability of the colored photosensitive composition is further improved, a development accelerator may be added. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1,000 or less and a low molecular weight phenol compound having a molecular weight of 1,000 or less.

具體而言，例如可列舉：甲酸、乙酸、丙酸、丁酸、戊酸、特戊酸、己酸、二乙基乙酸、庚酸、辛酸等脂肪族單羧酸；乙二酸、丙二酸、丁二酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十三烷二酸(brassylic acid)、甲基丙二酸、乙基丙二酸、二甲基丙二酸、甲基丁二酸、四甲基丁二酸、檸康酸等脂肪族二羧酸；1,2,3-丙三甲酸(tricarballylic acid)、烏頭酸(aconitic acid)、降莰三酸(camphoronic acid)等脂肪族三羧酸；苯甲酸、甲苯甲酸(toluic acid)、茴香甲酸(cumic acid)、2,3-二甲基苯甲酸(hemellitic acid)、3,5-二甲基苯甲酸(mesitylenic acid) 等芳香族單羧酸；鄰苯二甲酸、間苯二甲酸、對苯二甲酸、偏苯三甲酸(trimellitic acid)、均苯三甲酸(trimesic acid)、1,2,3,5-苯四甲酸(mellophanic acid)、均苯四甲酸(pyromellitic acid)等芳香族聚羧酸；苯基乙酸、氫化阿托酸(hydratropic acid)、氫化桂皮酸(hydrocinnamic acid)、苦杏仁酸(mandelic acid)、苯基丁二酸、阿托酸、桂皮酸、桂皮酸甲酯、桂皮酸苄酯、亞桂皮基乙酸(cinnamylidene acetic acid)、香豆酸(coumaric acid)、傘形酸(umbellic acid)等。 Specific examples thereof include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, heptanoic acid, and caprylic acid; and oxalic acid and propylene glycol; Acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, trisallic acid, methylmalonic acid, ethylpropane Aliphatic dicarboxylic acid such as acid, dimethylmalonic acid, methyl succinic acid, tetramethyl succinic acid, citraconic acid; 1,2,3-propane tricarboxylic acid (tricarballylic acid), aconitic acid (aconic acid) Acid), aliphatic tricarboxylic acid such as camphoronic acid; benzoic acid, toluic acid, cumic acid, 2,3-dimethylbenzoic acid, 3 ,5-dimethylbenzoic acid (mesitylenic acid) Equivalent aromatic monocarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, 1,2,3,5-benzene An aromatic polycarboxylic acid such as melophanic acid or pyromellitic acid; phenylacetic acid, hydratropic acid, hydrocinnamic acid, mandelic acid, Phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umbellic acid, and the like.

(其他添加物) (other additives)

本發明的著色感光性組成物中，進而可視需要而調配各種添加物，例如：填充劑、上述以外的高分子化合物、紫外線吸收劑、抗氧化劑等。該些添加物可列舉日本專利特開2004-295116號公報的段落[0155]~[0156]中記載的添加物。 In the colored photosensitive composition of the present invention, various additives such as a filler, a polymer compound other than the above, an ultraviolet absorber, an antioxidant, and the like may be blended as needed. Examples of the additives include the additives described in paragraphs [0155] to [0156] of JP-A-2004-295116.

本發明的著色感光性組成物中，可含有日本專利特開2004-295116號公報的段落[0078]中記載的光穩定劑、該公報的段落[0081]中記載的熱聚合防止劑。 The coloring photosensitive composition of the present invention may contain the light stabilizer described in paragraph [0078] of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph [0081] of the publication.

(著色感光性組成物的製備方法) (Preparation method of coloring photosensitive composition)

本發明的著色感光性組成物是藉由將上述各成分與視需要的任意成分混合而製備。較佳為藉由使用上述分散組成物作為著色劑成分，將上述各成分與視需要的任意成分混合而製備。 The colored photosensitive composition of the present invention is prepared by mixing the above components with optional optional components. It is preferred to prepare the above components by mixing them with any optional components as necessary by using the above-mentioned dispersion composition as a colorant component.

此外，製備著色感光性組成物時，可將構成著色感光性 組成物的各成分總括調配，亦可逐次調配。另外，調配時的投入順序或作業條件不受特別制約。 In addition, when the coloring photosensitive composition is prepared, the coloring sensitivity can be formed. The components of the composition are collectively formulated and may be dispensed one by one. In addition, the order of input or the working conditions at the time of preparation are not particularly restricted.

以上述方式製備的著色感光性組成物較佳為可使用孔徑為0.01 μm~3.0 μm左右的過濾器等進行過濾分離後，供於使用。 The colored photosensitive composition prepared as described above is preferably used by being filtered and separated using a filter having a pore diameter of about 0.01 μm to 3.0 μm.

本發明的著色感光性組成物可形成耐熱性優異、對比度優異的著色硬化膜，因此可適宜用於形成液晶顯示裝置中使用的彩色濾光片等的著色畫素，另外，可適宜用作印刷油墨、噴墨油墨、及塗料等的製作用途。 The colored photosensitive composition of the present invention can form a colored cured film having excellent heat resistance and excellent contrast, and therefore can be suitably used for forming a colored pixel such as a color filter used in a liquid crystal display device, and can be suitably used for printing. Production of inks, inkjet inks, and coatings.

《彩色濾光片及其製造方法》 "Color filter and its manufacturing method"

本發明的彩色濾光片是設置支持體，且在該支持體上設置包含本發明著色感光性組成物的著色區域來構成。支持體上的著色區域包含形成彩色濾光片的各畫素的例如紅(R)、綠(G)、藍(B)等著色層。 The color filter of the present invention is provided with a support, and a colored region including the colored photosensitive composition of the present invention is provided on the support. The colored region on the support includes colored layers such as red (R), green (G), and blue (B) which form respective pixels of the color filter.

本發明的彩色濾光片的製造方法包括以下步驟：著色層形成步驟(A)，將所述著色感光性組成物塗佈於支持體上而形成著色層(著色感光性組成物層)；曝光步驟(B)，對由步驟(A)形成的著色層進行圖案式樣的曝光；以及顯影步驟(C)，將上述經曝光的著色層進行顯影而形成著色圖案。 The method for producing a color filter of the present invention comprises the steps of: a colored layer forming step (A), applying the colored photosensitive composition onto a support to form a colored layer (colored photosensitive composition layer); and exposing Step (B), performing patterning exposure on the coloring layer formed by the step (A); and developing step (C), developing the exposed coloring layer to form a colored pattern.

另外，本發明的彩色濾光片的製造方法中，特佳為進而設置有對步驟(C)中獲得的著色圖案進行加熱處理的步驟(D) 的實施方式。 Further, in the method for producing a color filter of the present invention, it is particularly preferable to further provide a step (D) of heat-treating the coloring pattern obtained in the step (C). Implementation.

以下，對本發明的彩色濾光片的製造方法進行更具體的說明。 Hereinafter, a method of producing the color filter of the present invention will be described more specifically.

-步驟(A)- -Step (A)-

本發明的彩色濾光片的製造方法中，首先在支持體上，利用旋轉塗佈、狹縫塗佈、流延塗佈、輥塗佈、棒塗佈、噴墨等塗佈方法來塗佈所述本發明的著色感光性組成物而形成著色層，然後，藉由加熱(預烤(prebake))或真空乾燥等使該著色層乾燥。 In the method for producing a color filter of the present invention, first, coating is applied to a support by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, or inkjet. The colored photosensitive composition of the present invention forms a colored layer, and then the colored layer is dried by heating (prebake) or vacuum drying.

支持體例如可列舉液晶顯示裝置中使用的鈉玻璃、無鹼玻璃、硼矽酸玻璃、石英玻璃、矽基板、樹脂基板等。另外，該些支持體上，視需要為了改良與上部的層的密接、防止物質的擴散、或者為了表面的平坦化，亦可設置底塗層。 Examples of the support include soda glass, alkali-free glass, borosilicate glass, quartz glass, a ruthenium substrate, and a resin substrate used in a liquid crystal display device. Further, on these supports, an undercoat layer may be provided in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface as needed.

預烤的條件可列舉使用加熱板或烘箱，在70℃~130℃下加熱0.5分鐘~15分鐘左右的條件。 The pre-baking conditions may be, for example, heating at 70 ° C to 130 ° C for 0.5 minutes to 15 minutes using a hot plate or an oven.

另外，利用著色感光性組成物來形成的著色層的厚度是根據目的來適當選擇。液晶顯示裝置用彩色濾光片中，較佳為0.2 μm~5.0 μm的範圍，尤佳為1.0 μm~4.0 μm的範圍。此外，著色層的厚度為乾燥後的膜厚。 Further, the thickness of the coloring layer formed by the coloring photosensitive composition is appropriately selected depending on the purpose. The color filter for a liquid crystal display device preferably has a range of 0.2 μm to 5.0 μm, and more preferably 1.0 μm to 4.0 μm. Further, the thickness of the colored layer is the film thickness after drying.

-步驟(B)- -Step (B)-

繼而，本發明的彩色濾光片的製造方法中，對形成於支持體上的著色層進行圖案式樣的曝光。可應用於曝光的光或者放 射線較佳為g線、h線、i線、各種雷射光，特佳為i線。在將高壓水銀燈用於照射光的情況下，較佳為以5 mJ/cm2~500 mJ/cm2的曝光量進行照射。 Then, in the method of producing a color filter of the present invention, the coloring layer formed on the support is subjected to pattern pattern exposure. The light or radiation that can be applied to the exposure is preferably a g-line, an h-line, an i-line, or various kinds of laser light, and particularly preferably an i-line. In the case where a high pressure mercury lamp is used for the irradiation of light, it is preferably irradiated with an exposure amount of 5 mJ/cm 2 to 500 mJ/cm 2 .

另外，其他曝光光源可使用：超高壓、高壓、中壓、低壓的各水銀燈，化學燈(chemical lamp)、碳弧燈(carbon arc lamp)、氙燈(xenon lamp)、金屬鹵化物燈(metal halide lamp)、各種雷射光源等。 In addition, other exposure light sources can be used: ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps. Lamp), various laser light sources, etc.

~使用雷射光源的曝光步驟~ ~ Exposure step using a laser source~

使用雷射光源的曝光方式中，照射光較佳為波長為300 nm~410 nm範圍的波長範圍的紫外光雷射，尤佳為300 nm~360 nm範圍的波長。具體而言，尤其可適宜使用功率大且比較廉價的固體雷射的摻雜釹的釔鋁石榴石(neodymium doped yttrium aluminum garnet，Nd：YAG)雷射的第三諧波(355 nm)、或準分子雷射的XeCl(308 nm)、XeF(353 nm)。就生產性的觀點而言，圖案曝光量較佳為1 mJ/cm2~100 mJ/cm2的範圍，更佳為1 mJ/cm2~50 mJ/cm2的範圍。 In the exposure mode using a laser light source, the illumination light is preferably an ultraviolet laser having a wavelength in the range of 300 nm to 410 nm, and particularly preferably a wavelength in the range of 300 nm to 360 nm. In particular, it is particularly suitable to use a third harmonic (355 nm) of a neon-doped yttrium aluminum garnet (Nd:YAG) laser of a solid laser which is relatively expensive and relatively inexpensive, or Excimer laser XeCl (308 nm), XeF (353 nm). The pattern exposure amount is preferably in the range of 1 mJ/cm 2 to 100 mJ/cm 2 from the viewpoint of productivity, and more preferably in the range of 1 mJ/cm 2 to 50 mJ/cm 2 .

曝光裝置並無特別限制，市售的曝光裝置可使用Callisto(V科技(V-Technology)股份有限公司製造)、EGIS(V科技股份有限公司製造)或DF2200G(大日本絲網股份有限公司製造)等。另外，上述以外的裝置亦可適宜使用。 The exposure apparatus is not particularly limited, and a commercially available exposure apparatus can be used by Callisto (manufactured by V-Technology Co., Ltd.), EGIS (manufactured by V Technology Co., Ltd.), or DF2200G (manufactured by Dainippon Wire Mesh Co., Ltd.). Wait. Further, devices other than the above may be suitably used.

-步驟(C)- -Step (C)-

繼而，利用顯影液，對曝光後的著色層進行顯影。藉此可形成著色圖案。顯影液只要是溶解著色層的未硬化部，且不溶解硬化部的顯影液，則可使用多種有機溶劑的組合或鹼性水溶液。在顯影液為鹼性水溶液的情況下，鹼濃度宜以pH較佳為成為10~13的方式進行調整。上述鹼性水溶液例如可列舉氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氨水、乙基胺、二乙基胺、二甲基乙醇胺、四甲基氫氧化銨、四乙基氫氧化銨、膽鹼(choline)、吡咯、哌啶、1,8-二氮雜雙環-[5,4,0]-7-十一烯(1,8-diazabicyclo-[5,4,0]-7-undecene)等鹼性水溶液。 Then, the exposed coloring layer is developed using a developing solution. Thereby, a colored pattern can be formed. The developer may be a combination of a plurality of organic solvents or an alkaline aqueous solution as long as it dissolves the uncured portion of the colored layer and does not dissolve the developer of the cured portion. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted so that the pH is 10 to 13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, and tetramethyl. Ammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecene (1,8-diazabicyclo -[5,4,0]-7-undecene) and other alkaline aqueous solutions.

顯影時間較佳為30秒~300秒，尤佳為30秒~120秒。顯影溫度較佳為20℃~40℃，尤佳為23℃。 The development time is preferably from 30 seconds to 300 seconds, and particularly preferably from 30 seconds to 120 seconds. The developing temperature is preferably from 20 ° C to 40 ° C, particularly preferably 23 ° C.

顯影可以攪拌(puddle)方式、噴淋方式、噴射(spray)方式等來進行。 The development can be carried out by a puddle method, a shower method, a spray method, or the like.

另外，使用鹼性水溶液進行顯影後，較佳為以水清洗。 Further, after development using an aqueous alkaline solution, it is preferably washed with water.

本發明的彩色濾光片的製造方法中，亦特佳為對使用著色感光性組成物而形成的著色圖案(畫素)進行藉由紫外線照射的後曝光。 In the method for producing a color filter of the present invention, it is particularly preferable to perform post-exposure by ultraviolet irradiation on a coloring pattern (pixel) formed using a coloring photosensitive composition.

-步驟(D)- -Step (D)-

較佳為對顯影後的著色圖案，或者對已進行如上所述的藉由紫外線照射的後曝光的著色圖案，進一步進行加熱處理。藉由對所形成的著色圖案進行加熱處理(所謂後烘烤處理)，可使著 色圖案進一步硬化。該加熱處理例如可利用加熱板、各種加熱器、烘箱等來進行。 It is preferable to further heat-treat the colored pattern after development or the colored pattern which has been subjected to post-exposure by ultraviolet irradiation as described above. By heating the formed color pattern (so-called post-baking treatment), The color pattern is further hardened. This heat treatment can be performed, for example, using a hot plate, various heaters, an oven, or the like.

加熱處理時的溫度較佳為100℃~300℃，尤佳為150℃~250℃。另外，加熱時間較佳為10分鐘~120分鐘左右。 The temperature during the heat treatment is preferably from 100 ° C to 300 ° C, particularly preferably from 150 ° C to 250 ° C. Further, the heating time is preferably from about 10 minutes to about 120 minutes.

以上述方式獲得的著色圖案構成彩色濾光片中的綠色畫素。製作具有多種色相的畫素的彩色濾光片時，只要根據所需的色數來重複上述步驟(A)、步驟(B)、步驟(C)以及步驟(D)即可。 The colored pattern obtained in the above manner constitutes a green pixel in the color filter. When a color filter having a plurality of hues of pixels is produced, the above steps (A), (B), (C), and (D) may be repeated in accordance with the desired number of colors.

此外，可在每次單色著色層的形成、曝光、顯影結束時(每1色)進行上述步驟(D)，亦可在所需色數的所有著色層的形成、曝光、顯影結束後總括地進行上述步驟(D)。 Further, the above step (D) may be performed every time the formation, exposure, and development of the monochromatic colored layer is completed (per color), or after the formation, exposure, and development of all the colored layers of the desired color number are completed. The above step (D) is carried out.

另外，本發明的著色感光性組成物可形成綠色的著色層，將綠色畫素設置於支持體上，但在著色畫素包含紅色藍色綠色的情況下，設置著色層的順序可為任一種順序。 Further, the colored photosensitive composition of the present invention can form a green coloring layer and set the green pixel on the support, but in the case where the colored pixel contains red, blue and green, the order of providing the colored layer can be any order.

《顯示裝置》 Display device

利用本發明的彩色濾光片的製造方法而獲得的彩色濾光片(本發明的彩色濾光片)由於使用本發明的著色感光性組成物，故而耐熱性及對比度優異。 The color filter (the color filter of the present invention) obtained by the method for producing a color filter of the present invention is excellent in heat resistance and contrast because the coloring photosensitive composition of the present invention is used.

本發明的顯示裝置包括本發明的彩色濾光片。 The display device of the present invention includes the color filter of the present invention.

具體而言，本發明的顯示裝置較佳為：液晶顯示器(液晶顯示裝置，liquid crystal display，LCD)、有機電激發光 (electroluminescence，EL)顯示器(有機EL顯示裝置)、液晶投影儀、遊戲機用顯示裝置、行動電話等行動終端用顯示裝置、數位照相機用顯示裝置、汽車導航用顯示裝置等顯示裝置，特別適宜為彩色顯示裝置。 Specifically, the display device of the present invention is preferably: a liquid crystal display (liquid crystal display, LCD), organic electroluminescence (electroluminescence, EL) display (organic EL display device), liquid crystal projector, display device for game machine, display device for mobile terminal such as mobile terminal, display device for digital camera, display device for car navigation, etc., particularly suitable for Color display device.

在將本發明的彩色濾光片用於有機EL顯示裝置、或液晶顯示裝置等的情況下，不僅達成良好的色相，而且可顯示分光特性及對比度優異的影像。 When the color filter of the present invention is used in an organic EL display device or a liquid crystal display device or the like, not only a good hue but also an image excellent in spectral characteristics and contrast can be displayed.

〈液晶顯示裝置〉 <Liquid crystal display device>

對使用本發明彩色濾光片的液晶顯示裝置進行說明。關於有機EL顯示裝置或液晶顯示裝置的定義或各顯示裝置的詳情，例如記載於「電子顯示裝置(佐佐木昭夫著，(股)工業調査會1990年發行)」、「顯示裝置(伊吹順章著，產業圖書(股)1989年發行)」等中。另外，關於液晶顯示裝置，例如記載於「下一代液晶顯示器技術(內田龍男編輯，(股)工業調査會1994年發行)」中。對本發明可應用的液晶顯示裝置並無特別限制，例如可應用上述「下一代液晶顯示器技術」中記載的多種方式的液晶顯示裝置。 A liquid crystal display device using the color filter of the present invention will be described. The definition of the organic EL display device or the liquid crystal display device or the details of each display device is described, for example, in "Electronic display device (sasaki Sasaki, Ltd., issued by the Industrial Research Association in 1990)" and "display device (Ibuki Shunzhang) , Industrial Books (shares issued in 1989)" and so on. In addition, the liquid crystal display device is described in, for example, "Next-Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Industrial Research Association, 1994)". The liquid crystal display device to which the present invention is applicable is not particularly limited, and for example, various types of liquid crystal display devices described in the "Next Generation Liquid Crystal Display Technology" can be applied.

其中，本發明的彩色濾光片尤其對彩色薄膜電晶體(thin film transistor，TFT)方式的液晶顯示裝置有效。關於彩色TFT方式的液晶顯示裝置，例如記載於「彩色TFT液晶顯示器(共立出版(股)1996年發行)」中。進而，本發明亦可應用於橫向電場 切換(in-plane switching，IPS)等橫向電場驅動方式、多象限垂直配向(multi-domain vertical alignment，MVA)等畫素分期方式等視角擴大的液晶顯示裝置，或超扭轉向列(super twisted nematic，STN)、扭轉向列(twisted nematic，TN)、垂直配向(vertical alignment，VA)、光學補償傾斜(optically compensated splay，OCS)、邊緣場切換(fringe field switching，FFS)、及反射光學補償彎曲(reflective optically compensated bend，R-OCB)等。另外，本發明的彩色濾光片亦可提供給彩色濾光片陣列(color-filter on array，COA)方式。 Among them, the color filter of the present invention is particularly effective for a thin film transistor (TFT) type liquid crystal display device. A liquid crystal display device of a color TFT type is described, for example, in "Color TFT Liquid Crystal Display (Kyoritsu Publishing Co., Ltd., 1996)". Furthermore, the present invention can also be applied to a transverse electric field A liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as in-plane switching (IPS) or a multi-domain vertical alignment (MVA), or a super twisted nematic (super twisted nematic) , STN), twisted nematic (TN), vertical alignment (VA), optically compensated splay (OCS), fringe field switching (FFS), and optical compensation for bending (reflective optically compensated bend, R-OCB) and the like. In addition, the color filter of the present invention can also be provided to a color-filter on array (COA) method.

若將本發明的彩色濾光片用於液晶顯示裝置，則與先前公知的冷陰極管的三波長管組合時可實現高對比度，進而，藉由將紅、綠、藍的LED光源(RGB-LED)作為背光源，可提供亮度高，並且色純度高的色再現性良好的液晶顯示裝置。 When the color filter of the present invention is used in a liquid crystal display device, high contrast can be achieved when combined with a three-wavelength tube of a conventionally known cold cathode tube, and further, by using red, green, and blue LED light sources (RGB- As a backlight, LED) can provide a liquid crystal display device having high luminance and high color reproducibility.

[實施例] [Examples]

以下，利用實施例來對本發明進一步進行具體說明，但並不限定於以下的實施例。此外，只要無特別說明，則「%」、「份」為質量基準。 Hereinafter, the present invention will be specifically described by way of examples, but it is not limited to the following examples. In addition, "%" and "parts" are quality standards unless otherwise specified.

[實施例1-1] [Example 1-1] -綠色分散組成物1的製備- - Preparation of green dispersion composition 1 - 〈有色材料組成物的製備〉 <Preparation of Composition of Colored Materials>

將市售的C.I.顏料綠58(製品名：DIC股份有限公司製 造，FASTGEN GREEN A110)100份、染料Y1(下述結構)50份、氯化鈉400份、以及水溶性有機溶劑二乙二醇140份加入至桌上型捏合機((股)入江商會製造)中，混練10小時。繼而將該混練物在溶解器((股)日本精機製作所製造)中與水攪拌、混合後，反覆進行過濾、水洗而去除氯化鈉及溶劑，獲得有色材料的濾餅。然後，使該濾餅在80℃的烘箱中乾燥6小時，獲得C.I.顏料綠58與染料Y1的有色材料組成物。 Commercially available C.I. Pigment Green 58 (product name: DIC Corporation) 100 parts of FASTGEN GREEN A110), 50 parts of dye Y1 (structure described below), 400 parts of sodium chloride, and 140 parts of water-soluble organic solvent diethylene glycol were added to a table-type kneader (made by the company) ), mixing for 10 hours. Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a colored material composition of C.I. Pigment Green 58 and Dye Y1.

〈粗分散〉 Rough dispersion

使用上述有色材料組成物，以下述的組成進行調合後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.8 mm的氧 化鋯珠粒，將混合物分散。 Using the above-mentioned colored material composition, after blending with the following composition, Eiger-mill (manufactured by Eiger, Japan) and oxygen having a diameter of 0.8 mm were used. The zirconium beads were dispersed and the mixture was dispersed.

．有色材料組成物： 150份 . Colored material composition: 150 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

．有機溶劑：丙二醇單甲醚乙酸酯 220份 . Organic solvent: propylene glycol monomethyl ether acetate 220 parts

〈精密分散〉 <Precision dispersion>

取出上述粗分散後的分散物，相對於分散物100份而添加丙二醇單甲醚乙酸酯30份，進行混合。然後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.1 mm的氧化鋯珠粒進行分散。 The above-mentioned coarsely dispersed dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion, and the mixture was mixed. Then, dispersion was carried out using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

〈濃度調整〉 <concentration adjustment>

取出精密分散後的分散物，以顏料濃度達到10%的方式添加丙二醇單甲醚乙酸酯來稀釋，製成綠色分散組成物1。 The finely dispersed dispersion was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a green dispersion composition 1.

-著色感光性組成物的製備- - Preparation of coloring photosensitive composition -

將下述各成分混合、溶解，來製備著色感光性組成物11。 The coloring photosensitive composition 11 was prepared by mixing and dissolving each component mentioned below.

．有機溶劑1：丙二醇單甲醚乙酸酯 29份 . Organic solvent 1: propylene glycol monomethyl ether acetate 29 parts

．有機溶劑2：二乙二醇乙基甲醚 26份 . Organic solvent 2: diethylene glycol ethyl methyl ether 26 parts

．鹼可溶性黏合劑1：甲基丙烯酸環己酯/甲基丙烯酸/ 甲基丙烯酸環氧丙酯(=莫耳比：30/30/40)的甲基丙烯酸的加成物(45%丙二醇單甲醚溶液) 7份 . Alkali Soluble Binder 1: Cyclohexyl Methacrylate / Methacrylic Acid / Adduct of methacrylic acid methacrylate (= molar ratio: 30/30/40) (45% propylene glycol monomethyl ether solution) 7 parts

．鹼可溶性黏合劑2：甲基丙烯酸烯丙酯/甲基丙烯酸共聚物=莫耳比70/30(重量平均分子量26800) 6份 . Alkali-soluble binder 2: allyl methacrylate / methacrylic acid copolymer = molar ratio 70 / 30 (weight average molecular weight 26800) 6 parts

．聚合性化合物1：日本化藥(股)製造，KAYARAD DPHA 4份 . Polymeric Compound 1: Made by Nippon Chemical Co., Ltd., KAYARAD DPHA 4 parts

．聚合性化合物2：東亞合成(股)製造，Aronix TO-2349 4份 . Polymeric Compound 2: East Asian Synthetic (Stock), Aronix TO-2349 4 parts

．聚合抑制劑：對甲氧基苯酚 0.003份 . Polymerization inhibitor: p-methoxyphenol 0.003 parts

．光聚合起始劑1：1-(O-乙醯基肟)-1-[9-乙基-6-(硫苯醯基)-9H-咔唑-3-基]丙酮 0.3份 . Photopolymerization initiator: 1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylhydrazinyl)-9H-indazol-3-yl]acetone 0.3 parts

．光聚合起始劑2：1,3-二氫-1-苯基-2H-苯并咪唑-2-硫酮 0.2份 . Photopolymerization initiator 2: 1,3-dihydro-1-phenyl-2H-benzimidazole-2-thione 0.2 parts

．多官能硫醇化合物：1,4-雙(3-巰基丁醯氧基)丁烷 0.1份 . Polyfunctional thiol compound: 1,4-bis(3-mercaptobutoxy)butane 0.1 part

．密接改良劑：3-甲基丙烯醯氧基丙基三甲氧基矽烷 0.2份 . Adhesive improver: 3-methacryloxypropyltrimethoxydecane 0.2 parts

．氟系界面活性劑：DIC公司製造的Megafac F-554(0.2%丙二醇單甲醚乙酸酯溶液) 5份 . Fluorine-based surfactant: Megafac F-554 (0.2% propylene glycol monomethyl ether acetate solution) manufactured by DIC Corporation 5 parts

．綠色分散組成物1 30份 . Green dispersion composition 1 30 parts

[實施例1-2~實施例1-6] [Example 1-2 to Example 1-6]

實施例1-1中，除了將用於製備有色材料組成物的染料變更為如表1所記載以外，以與實施例1-1相同的方式製成著色感光性組成物1-2~著色感光性組成物1-6。 In Example 1-1, a coloring photosensitive composition 1-2 was colored in the same manner as in Example 1-1, except that the dye for preparing a colored material composition was changed as shown in Table 1. Sex composition 1-6.

此外，實施例1-2~實施例1-24中使用的染料如下所述。 Further, the dyes used in Examples 1-2 to 1-24 are as follows.

[實施例1-7] [Examples 1-7] -綠色分散組成物7的製備- - Preparation of green dispersion composition 7 - 〈顏料的微細化〉 <Micronization of Pigments>

將100份的實施例1-1中使用的C.I.顏料綠58、氯化鈉400份、以及二乙二醇140份加入至桌上型捏合機((股)入江商會製造)中，混練10小時。繼而將該混練物在溶解器((股)日本精機製作所製造)中與水攪拌、混合後，反覆進行過濾、水洗而去除氯化鈉及溶劑，獲得有色材料的濾餅。然後，使該濾餅在80℃的烘箱中乾燥6小時，獲得C.I.顏料綠58的微細化顏料。 100 parts of CI Pigment Green 58 used in Example 1-1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were added to a table type kneader (manufactured by the company), and kneaded for 10 hours. . Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Green 58.

〈粗分散〉 Rough dispersion

使用上述微細化顏料，以下述的組成進行調合後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.8 mm的氧化鋯珠粒，將混合物分散。 Using the above-described fine pigment, the mixture was blended in the following composition, and then the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

．微細化顏料 100份 . Micronized pigment 100 parts

．染料Y1(上述化合物)的7.5%丙二醇單甲醚乙酸酯溶液 667份 . 7.5% propylene glycol monomethyl ether acetate solution of dye Y1 (the above compound) 667 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

〈精密分散〉 <Precision dispersion>

取出上述粗分散後的分散物，然後，使用Eiger-mill(日 本艾格爾(股)製造)與直徑為0.1 mm的氧化鋯珠粒進行分散。 The above coarsely dispersed dispersion was taken out, and then, Eiger-mill was used. Ben Aeger (manufactured by the company) is dispersed with zirconia beads having a diameter of 0.1 mm.

〈濃度調整〉 <concentration adjustment>

取出上述精密分散後的分散物，以顏料濃度達到10%的方式添加丙二醇單甲醚乙酸酯來稀釋，製成綠色分散組成物7。 The finely dispersed dispersion was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a green dispersion composition 7.

-著色感光性組成物1-7的製備- - Preparation of coloring photosensitive composition 1-7 -

實施例1-1中，除了將綠色分散組成物1替代為綠色分散組成物7以外，以與實施例1-1相同的方式製作著色感光性組成物1-7。 In the Example 1-1, the colored photosensitive composition 1-7 was produced in the same manner as in Example 1-1, except that the green dispersion composition 1 was replaced with the green dispersion composition 7.

[實施例1-8~實施例1-12] [Examples 1-8 to 1-12]

實施例1-7中，除了將粗分散中所添加的染料變更為如表1中所記載以外，以與實施例1-7相同的方式製成著色感光性組成物1-8~著色感光性組成物1-12。 In Example 1-7, the coloring photosensitive composition 1-8 was colored in the same manner as in Example 1-7 except that the dye added in the coarse dispersion was changed as described in Table 1. Composition 1-12.

[實施例1-13] [Examples 1-13] -綠色分散組成物13的製備- - Preparation of green dispersion composition 13 - 〈顏料的微細化〉 <Micronization of Pigments>

將100份的實施例1-1中使用的C.I.顏料綠58、氯化鈉400份、以及二乙二醇140份加入至桌上型捏合機((股)入江商會製造)中，混練10小時。繼而將該混練物在溶解器((股)日本精機製作所製造)中與水攪拌、混合後，反覆進行過濾、水洗而去除氯化鈉及溶劑，獲得有色材料的濾餅。然後，使該濾餅在80℃的烘箱中乾燥6小時，獲得C.I.顏料綠58的微細化顏料。 100 parts of CI Pigment Green 58 used in Example 1-1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were added to a table type kneader (manufactured by the company), and kneaded for 10 hours. . Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Green 58.

〈粗分散〉 Rough dispersion

使用上述微細化顏料，以下述的組成進行調合後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.8 mm的氧化鋯珠粒，將混合物分散。此時，最初以粉狀態將微細化顏料與染料混合，繼而添加其他材料來進行分散。 Using the above-described fine pigment, the mixture was blended in the following composition, and then the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm. At this time, the fine pigment is first mixed with the dye in a powder state, and then other materials are added to be dispersed.

．微細化顏料： 100份 . Micronized pigment: 100 parts

．染料Y1： 50份 . Dye Y1: 50 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

．有機溶劑：丙二醇單甲醚乙酸酯 220份 . Organic solvent: propylene glycol monomethyl ether acetate 220 parts

〈精密分散〉 <Precision dispersion>

取出上述粗分散後的分散物，相對於分散物100份而添加丙二醇單甲醚乙酸酯30份，進行混合。然後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.1 mm的氧化鋯珠粒進行分散。 The above-mentioned coarsely dispersed dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion, and the mixture was mixed. Then, dispersion was carried out using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

〈濃度調整〉 <concentration adjustment>

取出上述精密分散後的分散組成物，以顏料濃度達到10%的方式添加丙二醇單甲醚乙酸酯來稀釋，製成綠色分散組成物13。 The finely dispersed dispersion composition was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a green dispersion composition 13.

-著色硬化性組成物1-13的製備- - Preparation of colored curable composition 1-13 -

實施例1-1中，除了代替綠色分散組成物1而使用綠色分散組成物13以外，以與實施例1-1相同的方式製作著色感光性組成物1-13。 In the Example 1-1, the colored photosensitive composition 1-13 was produced in the same manner as in Example 1-1, except that the green dispersion composition 13 was used instead of the green dispersion composition 1.

[實施例1-14~實施例1-18] [Examples 1-14 to 1-18]

實施例1-13中，除了將粗分散中所添加的染料變更為如表1中所記載以外，以與實施例1-13相同的方式製成著色感光性組成物1-14~著色感光性組成物1-18。 In Example 1-13, the coloring photosensitive composition 1-14 was colored in the same manner as in Example 1-13 except that the dye added in the coarse dispersion was changed as described in Table 1. Composition 1-18.

[實施例1-19] [Examples 1-19] -綠色分散組成物19的製備- - Preparation of green dispersion composition 19 - 〈顏料的微細化〉 <Micronization of Pigments>

將100份的實施例1-1中使用的C.I.顏料綠58、氯化鈉400份、以及二乙二醇140份加入至桌上型捏合機((股)入江商會製造)中，混練10小時。繼而將該混練物在溶解器((股)日本精機製作所製造)中與水攪拌、混合後，反覆進行過濾、水洗而去除氯化鈉及溶劑，獲得有色材料的濾餅。然後，使該濾餅在80℃的烘箱中乾燥6小時，獲得C.I.顏料綠58的微細化顏料。 100 parts of CI Pigment Green 58 used in Example 1-1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were added to a table type kneader (manufactured by the company), and kneaded for 10 hours. . Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Green 58.

〈粗分散〉 Rough dispersion

使用上述微細化顏料，以下述的組成進行調合後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.8 mm的氧化鋯珠粒，將混合物分散。 Using the above-described fine pigment, the mixture was blended in the following composition, and then the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

．微細化顏料： 100份 . Micronized pigment: 100 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

．丙二醇單甲醚乙酸酯 260份 . Propylene glycol monomethyl ether acetate 260 parts

〈精密分散〉 <Precision dispersion>

取出上述粗分散後的分散物，添加100份的分散物、及11份的染料Y1，進行混合。然後，添加丙二醇單甲醚乙酸酯30份，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.1 mm的氧化鋯珠粒進行分散。 The above-mentioned coarsely dispersed dispersion was taken out, and 100 parts of the dispersion and 11 parts of the dye Y1 were added and mixed. Then, 30 parts of propylene glycol monomethyl ether acetate was added, and dispersion was carried out using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm.

〈濃度調整〉 <concentration adjustment>

取出上述精密分散後的分散組成物，以顏料濃度達到10%的方式添加丙二醇單甲醚乙酸酯來稀釋，製成綠色分散組成物19。 The finely dispersed dispersion composition was taken out and diluted with propylene glycol monomethyl ether acetate so as to have a pigment concentration of 10% to prepare a green dispersion composition 19.

-著色感光性組成物1-19的製備- - Preparation of coloring photosensitive composition 1-19 -

實施例1-1中，除了將綠色分散組成物1替代為綠色分散組成物19以外，以與實施例1-1相同的方式製作著色感光性組成物1-19。 In the Example 1-1, the colored photosensitive composition 1-19 was produced in the same manner as in Example 1-1, except that the green dispersion composition 1 was replaced with the green dispersion composition 19.

[實施例1-20~實施例1-24] [Examples 1-20 to 1-24]

實施例1-19中，除了將精密分散時添加的染料變更為 如表1中所記載以外，以與實施例1-19相同的方式製作著色感光性組成物1-20~著色感光性組成物1-24。 In Examples 1-19, except that the dye added during the precise dispersion was changed to In the same manner as in Example 1-19, the colored photosensitive composition 1-20 to the colored photosensitive composition 1-24 was produced in the same manner as in Example 1-19.

[比較例1-1] [Comparative Example 1-1] -綠色分散組成物A的製備- - Preparation of green dispersion composition A - 〈顏料的微細化〉 <Micronization of Pigments>

將100份的實施例1-1中使用的C.I.顏料綠58、氯化鈉400份、以及二乙二醇140份加入至桌上型捏合機((股)入江商會製造)中，混練10小時。繼而將該混練物在溶解器((股)日本精機製作所製造)中與水攪拌、混合後，反覆進行過濾、水洗而去除氯化鈉及溶劑，獲得有色材料的濾餅。然後，使該濾餅在80℃的烘箱中乾燥6小時，獲得C.I.顏料綠58的微細化顏料。 100 parts of CI Pigment Green 58 used in Example 1-1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were added to a table type kneader (manufactured by the company), and kneaded for 10 hours. . Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Green 58.

〈粗分散〉 Rough dispersion

使用上述微細化顏料，以下述的組成進行調合後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.8 mm的氧化鋯珠粒，將混合物分散。 Using the above-described fine pigment, the mixture was blended in the following composition, and then the mixture was dispersed using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm.

．微細化顏料： 100份 . Micronized pigment: 100 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

．丙二醇單甲醚乙酸酯 260份 . Propylene glycol monomethyl ether acetate 260 parts

〈精密分散〉 <Precision dispersion>

取出上述粗分散後的分散物，相對於分散物100份而添加11份的染料Y1、以及丙二醇單甲醚乙酸酯19份，進行混合。然後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.1 mm的氧化鋯珠粒進行分散，獲得顏料濃度為10%的綠色分散組成物A。 The above-mentioned coarsely dispersed dispersion was taken out, and 11 parts of the dye Y1 and 19 parts of propylene glycol monomethyl ether acetate were added to 100 parts of the dispersion, followed by mixing. Then, dispersion was carried out using Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm to obtain a green dispersion composition A having a pigment concentration of 10%.

-著色感光性組成物A的製備- - Preparation of coloring photosensitive composition A -

實施例1-1中，除了將綠色分散組成物1變更為綠色分散組成物A以外，以與實施例1-1相同的方式製作著色感光性組成物A。 In the Example 1-1, the colored photosensitive composition A was produced in the same manner as in Example 1-1, except that the green dispersion composition 1 was changed to the green dispersion composition A.

[比較例1-2] [Comparative Example 1-2] 〈顏料的微細化〉 <Micronization of Pigments>

將100份的實施例1-1中使用的C.I.顏料綠58、氯化鈉400份、以及二乙二醇140份加入至桌上型捏合機((股)入江商會製造)中，混練10小時。繼而將該混練物在溶解器((股)日本精機製作所製造)中與水攪拌、混合後，反覆進行過濾、水洗而去除氯化鈉及溶劑，獲得有色材料的濾餅。然後，使該濾餅在80℃的烘箱中乾燥6小時，獲得C.I.顏料綠58的微細化顏料。 100 parts of CI Pigment Green 58 used in Example 1-1, 400 parts of sodium chloride, and 140 parts of diethylene glycol were added to a table type kneader (manufactured by the company), and kneaded for 10 hours. . Then, the kneaded product was stirred and mixed with water in a dissolver (manufactured by Nippon Seiki Co., Ltd.), and then filtered and washed with water to remove sodium chloride and a solvent to obtain a filter cake of a colored material. Then, the filter cake was dried in an oven at 80 ° C for 6 hours to obtain a fine pigment of C.I. Pigment Green 58.

〈粗分散〉 Rough dispersion

使用上述微細化顏料，以下述的組成進行調合後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.8 mm的氧化鋯珠 粒，將混合物分散。 Using the above-mentioned fine pigment, after blending with the following composition, Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.8 mm were used. Granules, dispersing the mixture.

．微細化顏料： 100份 . Micronized pigment: 100 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

．丙二醇單甲醚乙酸酯： 260份 . Propylene glycol monomethyl ether acetate: 260 parts

〈精密分散〉 <Precision dispersion>

取出上述粗分散後的分散物，相對於分散物100份而添加丙二醇單甲醚乙酸酯19份，進行混合。然後，使用Eiger-mill(日本艾格爾(股)製造)與直徑為0.1 mm的氧化鋯珠粒進行分散。分散後，添加11份的染料Y1，以三一馬達(Three-One Motor)進行混合，獲得綠色分散組成物B。 The above-mentioned coarsely dispersed dispersion was taken out, and 19 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion, followed by mixing. Then, dispersion was carried out using an Eiger-mill (manufactured by Eiger, Japan) and zirconia beads having a diameter of 0.1 mm. After the dispersion, 11 parts of the dye Y1 was added, and mixed with a Three-One Motor to obtain a green dispersion composition B.

-著色硬化性組成物B的製備- - Preparation of colored curable composition B -

實施例1-1中，除了將綠色分散組成物1變更為綠色分散組成物B以外，以與實施例1-1相同的方式製作著色感光性組成物B。 In the Example 1-1, the colored photosensitive composition B was produced in the same manner as in Example 1-1, except that the green dispersion composition 1 was changed to the green dispersion composition B.

[比較例1-3] [Comparative Example 1-3] -綠色分散組成物C的製備- - Preparation of green dispersion composition C -

以下述的組成進行調合後，使用塗料振盪器(成和技研(Seiwa Giken)製造)與直徑為0.1 mm的氧化鋯珠粒，將混合物 分散，獲得綠色分散組成物C。 After blending with the following composition, a mixture of a paint shaker (manufactured by Seiwa Giken) and zirconia beads having a diameter of 0.1 mm was used to mix the mixture. Dispersed to obtain a green dispersion composition C.

．實施例1-1中使用的C.I.顏料綠58： 100份 . C.I. Pigment Green 58: 100 parts used in Example 1-1

．染料Y1： 50份 . Dye Y1: 50 parts

．分散劑：Solsperse 22000(日本路博潤(股)製造) 10份 . Dispersant: Solsperse 22000 (made by Lubrizol, Japan) 10 parts

．分散劑：Solsperse 24000(日本路博潤(股)製造) 80份 . Dispersant: Solsperse 24000 (made by Lubrizol, Japan) 80 parts

．丙二醇單甲醚乙酸酯： 760份 . Propylene glycol monomethyl ether acetate: 760 parts

-著色感光性組成物C的製備- - Preparation of coloring photosensitive composition C -

實施例1-1中，除了將綠色分散組成物1變更為綠色分散組成物C以外，以與實施例1-1相同的方式製作著色感光性組成物C。 In the Example 1-1, the colored photosensitive composition C was produced in the same manner as in Example 1-1, except that the green dispersion composition 1 was changed to the green dispersion composition C.

以上述方式製作的著色感光性組成物中的Ci、Cf如下述所示。 The Ci and Cf in the coloring photosensitive composition produced in the above manner are as follows.

實施例1-1~實施例1-6中的Ci是根據預混合時的特定染料的濃度來計算，均為33.3%；Cf是根據分散結束後的濃度調整後的分散組成物中的染料的濃度來計算，實施例1-1~實施例1-6中均為5.0%。 The Ci in Examples 1-1 to 1-6 were calculated based on the concentration of the specific dye at the time of premixing, and both were 33.3%; Cf was the dye in the dispersed composition adjusted according to the concentration after the end of dispersion. The concentration was calculated to be 5.0% in each of Examples 1-1 to 1-6.

另外，實施例1-7~實施例1-18中的Ci是根據粗分散的組成來計算。實施例7~實施例12的Ci均為5.8%，實施例1-13~實施例1-18的Ci均為7.8%。Cf是根據分散結束後的濃度調整 後的分散組成物中的染料的濃度來計算，實施例1-7~實施例1-18中均為5.0%。 Further, Ci in Examples 1-7 to 1-18 was calculated based on the composition of the coarse dispersion. The Ci of Examples 7 to 12 were both 5.8%, and the Ci of Examples 1-13 to 1-18 were both 7.8%. Cf is adjusted according to the concentration after the end of dispersion The concentration of the dye in the subsequent dispersion composition was calculated to be 5.0% in each of Examples 1-7 to 1-18.

實施例1-19~實施例1-24中，Ci是根據精密分散的組成來計算，均為7.8%；Cf是根據分散結束後的濃度調整後的分散組成物中的染料的濃度來計算，均為5.0%。 In Examples 1-19 to 1-24, Ci was calculated based on the composition of the fine dispersion, and both were 7.8%; Cf was calculated based on the concentration of the dye in the dispersed composition after the concentration at the end of the dispersion. Both are 5.0%.

另外，比較例1-1~比較例1-3均為Ci=Cf，且均為5.0%。 Further, Comparative Example 1-1 to Comparative Example 1-3 were both Ci=Cf and both were 5.0%.

-評價- -Evaluation-

作為上述所得的著色感光性組成物1-1~著色感光性組成物1-24以及著色感光性組成物A~著色感光性組成物C的性能評價，以如下所示的方法對分光特性、對比度、耐熱性進行評價。另外，亦同時評價各綠色分散組成物中的對顏料的染料吸附率。評價結果示於表1中。 As a performance evaluation of the colored photosensitive composition 1-1 to the colored photosensitive composition 1-24 and the colored photosensitive composition A to the colored photosensitive composition C, the spectral characteristics and contrast were measured by the following method. Heat resistance was evaluated. Further, the dye adsorption ratio to the pigment in each of the green dispersion compositions was also evaluated. The evaluation results are shown in Table 1.

-著色感光性組成物層(著色層)的形成- - Formation of a coloring photosensitive composition layer (colored layer) -

在玻璃(#1737；道康寧(Dow Corning)公司製造)基板上，利用旋轉塗佈法來塗佈上述所製備的著色感光性組成物後，在室溫下乾燥30分鐘，藉此使揮發成分揮發而形成著色層。隔著細線圖案的遮罩，對該著色層照射i線(波長為365 nm)，形成潛像。i線的光源是使用超高壓水銀燈，形成平行光後再照射。此時，將照射光量設為40 mJ/cm2。繼而，對該形成有潛像的著色層，使用碳酸鈉/碳酸氫鈉的水溶液(濃度2.4%)，在26℃下顯影45秒，繼而，以流水淋洗20秒後，藉由噴射而乾燥，獲得細線圖 案影像。將所得的細線圖案影像在230℃下進行20分鐘後烘烤處理，獲得膜厚為2 μm的具有綠色細線圖案的著色層。 The colored photosensitive composition prepared above was applied onto a glass (#1737; manufactured by Dow Corning) substrate by a spin coating method, and then dried at room temperature for 30 minutes to volatilize volatile components. The color layer is formed. The colored layer was irradiated with an i-line (wavelength of 365 nm) through a mask of a thin line pattern to form a latent image. The light source of the i-line is an ultra-high pressure mercury lamp, which is formed by parallel light and then irradiated. At this time, the amount of irradiation light was set to 40 mJ/cm 2 . Then, the coloring layer on which the latent image was formed was developed using an aqueous solution of sodium carbonate/sodium hydrogencarbonate (concentration: 2.4%) at 26 ° C for 45 seconds, followed by rinsing with running water for 20 seconds, and then dried by spraying. , get a thin line pattern image. The obtained fine line pattern image was subjected to post-baking treatment at 230 ° C for 20 minutes to obtain a colored layer having a green fine line pattern having a film thickness of 2 μm.

(對比度評價) (contrast evaluation)

將具有所得著色層的基板夾持於2片偏光膜之間，使用色彩亮度計(拓普康(股)製造，型號：BM-5A)來測定2片偏光膜的偏光軸平行時、及垂直時的亮度的值，將2片偏光膜的偏光軸平行時的亮度除以垂直時的亮度，求出所得的值作為對比度。對比度越高，作為液晶顯示裝置用彩色濾光片而表現出越良好的性能。 The substrate having the obtained colored layer was sandwiched between two polarizing films, and a color luminance meter (manufactured by Topcon Co., model: BM-5A) was used to measure the polarization axes of the two polarizing films in parallel and perpendicularly. The value of the luminance at the time is obtained by dividing the luminance when the polarization axes of the two polarizing films are parallel by the luminance at the vertical, and obtaining the obtained value as the contrast. The higher the contrast, the better the performance as a color filter for a liquid crystal display device.

(分光特性) (Spectral characteristics)

使用顯微分光測定裝置(奧林巴斯(Olympus)(股)製造，型號OSP-SP200)來測定上述所得的著色層的穿透光譜。根據所得的穿透光譜，來求出CIE1931色彩系統(color specification system)中的色度座標x值、y值、Y值。 The transmission spectrum of the coloring layer obtained above was measured using a microscopic spectrometry apparatus (manufactured by Olympus Co., Ltd., model OSP-SP200). Based on the obtained breakthrough spectrum, the chromaticity coordinates x, y, and Y values in the CIE 1931 color specification system are obtained.

關於分光特性，在(x、y)=(0.300、0.600)中的Y值高的情況下，可以說具有優異的分光特性。Y值越大，可以說分光特性越優異。 Regarding the spectral characteristics, when the Y value in (x, y) = (0.300, 0.600) is high, it can be said that it has excellent spectral characteristics. The larger the Y value, the more excellent the spectral characteristics can be said.

(耐熱性) (heat resistance)

使用顯微分光測定裝置(奧林巴斯(股)製造，型號OSP-SP200)來測定上述所得著色層的穿透光譜後，在230℃下進行60分鐘追加烘烤，再次評價穿透光譜。計算追加烘烤前後的Y 值差(△Y)，將其作為耐熱性的指標。△Y越小，可以說耐熱性越優異。 The transmission spectrum of the obtained colored layer was measured using a microscopic spectrometry apparatus (manufactured by Olympus Co., Ltd., model OSP-SP200), and then baked at 230 ° C for 60 minutes to re-evaluate the breakthrough spectrum. Calculate Y before and after additional baking The value difference (ΔY) is used as an index of heat resistance. The smaller the ΔY, the more excellent the heat resistance.

(染料吸附率) (dye adsorption rate)

利用超離心分離機(日立工機(股)製造)，以50000 rpm對各綠色分散組成物進行離心處理，獲得包含游離成分的上清液。藉由HPLC來評價上清液中的染料量，由以下式子來定義吸附率。 Each green dispersion composition was centrifuged at 50,000 rpm by an ultracentrifuge (manufactured by Hitachi Koki Co., Ltd.) to obtain a supernatant containing a free component. The amount of the dye in the supernatant was evaluated by HPLC, and the adsorption rate was defined by the following formula.

根據表1的結果，可知以下情況。相對於比較例的著色感光性組成物A~著色感光性組成物C，本發明的著色感光性組成物1-1~著色感光性組成物1-24具有優異的耐熱性。耐熱性與染料吸附率相關，因此推定藉由在顏料上吸附有染料而抑制熱褪 色。本發明的顏料分散物由於染料吸附率提高，故而容易獲得高的耐熱性。 From the results of Table 1, the following can be seen. The colored photosensitive composition 1-1 to the colored photosensitive composition 1-24 of the present invention have excellent heat resistance with respect to the colored photosensitive composition A to the colored photosensitive composition C of the comparative example. Heat resistance is related to dye adsorption rate, so it is presumed to suppress heat fading by adsorbing dye on the pigment. color. Since the pigment dispersion of the present invention is improved in the dye adsorption rate, it is easy to obtain high heat resistance.

其原因被認為是由於在製作本發明的分散組成物時，投入染料時的染料濃度Ci高於最終的分散組成物中的染料濃度Cf。即認為，藉由以更高的濃度投入染料(例如，如實施例1-1所記載的顏料微細化時以固體狀態投入染料)而容易產生對顏料的吸附。 The reason for this is considered to be because the dye concentration Ci when the dye is introduced is higher than the dye concentration Cf in the final dispersion composition when the dispersion composition of the present invention is produced. In other words, it is considered that adsorption of the pigment is easily caused by the dye being introduced at a higher concentration (for example, when the pigment is added in a solid state when the pigment described in Example 1-1 is refined).

如比較例所示，於即便在分散步驟中投入，染料亦為低濃度的情況下，並且於如在分散步驟後單純地進行攪拌混合的情況下，染料吸附率低，因此耐熱性亦降低。 As shown in the comparative example, even when the dye was added at a low concentration in the dispersion step, and the mixture was simply stirred and mixed after the dispersion step, the dye adsorption rate was low, and thus the heat resistance was also lowered.

另外，令人驚訝的是，相對於比較例的著色感光性組成物A~著色感光性組成物C，本發明的著色感光性組成物1-1~著色感光性組成物1-24具有優異的對比度。其原因並不充分明確，但認為原因在於：由於在顏料表面吸附有染料，分散物中的游離的染料量少，故而製膜過程中的染料凝聚得到抑制。藉由染料的凝聚被抑制，成為光散射的原因的著色層中的粒子減少，因此推定對比度提高。 In addition, it is surprising that the coloring photosensitive composition A to the colored photosensitive composition C of the present invention is excellent in the coloring photosensitive composition A to the coloring photosensitive composition 1-24 of the comparative example. Contrast. The reason for this is not sufficiently clear, but it is considered that the reason is that since the dye is adsorbed on the surface of the pigment, the amount of free dye in the dispersion is small, so that the dye aggregation during the film formation is suppressed. Since the aggregation of the dye is suppressed, the particles in the coloring layer which is a cause of light scattering are reduced, and thus the contrast is estimated to be improved.

[實施例1-25] [Example 1-25] 〈液晶顯示裝置的製作〉 <Production of Liquid Crystal Display Device>

利用以下方法來製作彩色濾光片，製作使用該彩色濾光片的液晶顯示裝置來進行顯示特性的評價。 A color filter was produced by the following method, and a liquid crystal display device using the color filter was produced to evaluate display characteristics.

〈紅色著色感光性組成物R的製作〉 <Preparation of Red Colored Photosensitive Composition R>

將下述紅色顏料分散物組成進行混合，使用均質機，以轉速3,000 rpm攪拌3小時。進而藉由使用0.3 mm φ氧化鋯珠粒的珠粒分散機Dispermat(GETZMANN公司製造)，對以上述方式獲得的混合溶液進行12小時分散處理，然後，進而使用帶有減壓機構的高壓分散機NANO-3000-10(日本BEE(股)製造)，在2000 kg/cm3的壓力下設流量為500 g/min來進行分散處理。將該分散處理重複10次，獲得顏料分散組成物。 The following red pigment dispersion compositions were mixed and stirred using a homogenizer at 3,000 rpm for 3 hours. Further, the mixed solution obtained in the above manner was subjected to dispersion treatment for 12 hours by a bead disperser Dispermat (manufactured by GETZMANN) using 0.3 mm φ zirconia beads, and then, a high pressure dispersing machine with a pressure reducing mechanism was further used. NANO-3000-10 (manufactured by BEE Co., Ltd.) was subjected to dispersion treatment at a flow rate of 500 g/min under a pressure of 2000 kg/cm 3 . This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

[紅色顏料分散物組成] [Red pigment dispersion composition]

．C.I.顏料紅254 75份 . C.I. Pigment Red 254 75 parts

．C.I.顏料紅177 50份 . C.I. Pigment Red 177 50 parts

．甲基丙烯酸苄酯/甲基丙烯酸共聚物 70份(共聚合組成比70/30重量平均分子量30000，酸值40) . Benzyl methacrylate/methacrylic acid copolymer 70 parts (copolymerization composition ratio 70/30 weight average molecular weight 30000, acid value 40)

．丙二醇單甲醚乙酸酯 800份 . Propylene glycol monomethyl ether acetate 800 parts

於所得的顏料分散組成物中進而添加下述組成的成分，製作紅色感光性組成物R。 Further, a component having the following composition was further added to the obtained pigment dispersion composition to prepare a red photosensitive composition R.

[紅色感光性組成物R組成] [Red photosensitive composition R composition]

．上述紅色顏料分散物 100份 . The above red pigment dispersion 100 parts

．甲基丙烯酸苄酯/甲基丙烯酸(=70/30[莫耳比])共聚物(Mw：30,000)的丙二醇單甲醚乙酸酯溶液(固體成分為50%) 12份 . Benzyl methacrylate/methacrylic acid (=70/30 [mole ratio]) copolymer (Mw: 30,000) propylene glycol monomethyl ether acetate solution (solid content 50%) 12 parts

．聚合性化合物1：日本化藥(股)製造，KAYARAD DPHA 12.1份 . Polymeric Compound 1: Made by Nippon Chemical Co., Ltd., KAYARAD DPHA 12.1

．光聚合起始劑：2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物 3.1份 . Photopolymerization initiator: 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer 3.1 parts

．增感色素：4,4'-雙(二乙基胺基)二苯甲酮 4.2份 . Sensitizing pigment: 4,4'-bis(diethylamino)benzophenone 4.2 parts

．氫供與性化合物：2-巰基苯并噻唑 2.1份 . Hydrogen-donating compound: 2-mercaptobenzothiazole 2.1 parts

．聚合抑制劑：對甲氧基苯酚 0.001份 . Polymerization inhibitor: p-methoxyphenol 0.001 parts

．氟系界面活性劑(商品名：Megafac R08，DIC(股)製造) 0.5份 . Fluorine-based surfactant (trade name: Megafac R08, manufactured by DIC) 0.5 parts

．丙二醇單甲醚乙酸酯 60份 . Propylene glycol monomethyl ether acetate 60 parts

〈藍色感光性組成物B的製作〉 <Production of Blue Photosensitive Composition B>

於紅色著色感光性組成物R的製作中，除了代替C.I.顏料紅254而使用100份的C.I.顏料藍15：6，且代替C.I.顏料紅177而使用23份的C.I.顏料紫23以外，以相同的方式製作藍色感光性組成物B。 In the preparation of the red colored photosensitive composition R, 100 parts of CI Pigment Blue 15:6 was used instead of CI Pigment Red 254, and 23 parts of CI Pigment Violet 23 were used instead of CI Pigment Red 177, and the same The blue photosensitive composition B was produced in the same manner.

〈黑色感光性組成物K的製作〉 <Production of Black Photosensitive Composition K>

製備下述組成的顏料分散物組成，以與紅色顏料分散物製作時相同的方式進行分散處理，製作黑色顏料分散物。 A pigment dispersion composition having the following composition was prepared, and dispersion treatment was carried out in the same manner as in the preparation of the red pigment dispersion to prepare a black pigment dispersion.

[黑色顏料分散物組成] [Black pigment dispersion composition]

．碳黑(商品名：Nipex 35，日本德固賽(股)製造) 13.1份 . Carbon black (trade name: Nipex 35, manufactured by Degussa, Japan) 13.1 copies

．聚合物(甲基丙烯酸苄酯/甲基丙烯酸=72/28莫耳比的無規共聚物，分子量3.7萬) 6.7份 . Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio of random copolymer, molecular weight 37,000) 6.7 parts

．丙二醇單甲醚乙酸酯 79.1份 . Propylene glycol monomethyl ether acetate 79.1 parts

．分散劑(下述化合物) 0.65份 . Dispersing agent (the following compound) 0.65 parts

使用所得的黑色顏料分散物，以如下組成來製備調整黑色感光性組成物K。 Using the obtained black pigment dispersion, the black photosensitive composition K was prepared in the following composition.

[黑色感光性組成物K組成] [Black photosensitive composition K composition]

．上述黑色顏料分散物 25份 . The above black pigment dispersion 25 parts

．丙二醇單甲醚乙酸酯 8.5份 . Propylene glycol monomethyl ether acetate 8.5 parts

．甲基乙基酮 53份 . Methyl ethyl ketone 53 parts

．黏合劑：甲基丙烯酸苄酯/甲基丙烯酸=78/22莫耳比的無規共聚物(分子量3.8萬)27份與丙二醇單甲醚乙酸酯73份的混合物 9.1份 . Adhesive: benzyl methacrylate / methacrylic acid = 78 / 22 molar ratio random copolymer (molecular weight 38,000) 27 parts and propylene glycol monomethyl ether acetate 73 parts mixture 9.1 parts

．對苯二酚單甲醚 0.002份 . Hydroquinone monomethyl ether 0.002 parts

．聚合性化合物：DPHA(日本化藥公司製造) 12份 . Polymeric compound: DPHA (manufactured by Nippon Kayaku Co., Ltd.) 12 parts

．聚合起始劑：2,4-雙(三氯乙基)-6-[4'(N,N-雙乙氧基羰基甲基)胺基-3'-溴苯基]-均三嗪 0.16份 . Polymerization initiator: 2,4-bis(trichloroethyl)-6-[4'(N,N-diethoxycarbonylmethyl)amino-3'-bromophenyl]-s-triazine 0.16 Share

．界面活性劑(下述化合物)的甲基乙基酮30%溶液 0.042份 . Methyl ethyl ketone 30% solution of surfactant (the following compound) 0.042 parts

(n=6、x=55、y=5、Mw=33940、Mw/Mn=2.55 PO：環氧丙烷、EO：環氧乙烷) (n=6, x=55, y=5, Mw=33940, Mw/Mn=2.55 PO: propylene oxide, EO: ethylene oxide)

〈彩色濾光片的製作〉 <Production of Color Filters> 〈黑色矩陣的形成〉 <Formation of Black Matrix>

以紫外線(ultraviolet，UV)清洗裝置來清洗無鹼玻璃基板後，使用清洗劑進行刷洗，進而以超純水進行超音波清洗。將該基板在120℃下進行3分鐘熱處理，使表面狀態穩定化後，將該基板冷卻，調溫至23℃。 After cleaning the alkali-free glass substrate with an ultraviolet (UV) cleaning device, it is brushed with a cleaning agent, and ultrasonic cleaning is performed with ultrapure water. The substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state, and then the substrate was cooled and adjusted to 23 ° C.

於該基板上，利用具有狹縫狀噴嘴的玻璃基板用塗佈機(FAS亞洲(FAS Asia)公司製造，商品名：MH-1600)，塗佈上述黑色感光性組成物K。繼而利用VCD(真空乾燥裝置，東京應化工業(股)公司製造)，以30秒使溶劑的一部分乾燥來消除塗佈層的流動性，然後在120℃下預烤3分鐘，獲得膜厚為2.4 μm的黑色感光性組成物層。 The black photosensitive composition K was applied onto the substrate by a coating machine for a glass substrate (manufactured by FAS Asia, trade name: MH-1600) having a slit-like nozzle. Then, using a VCD (Vacuum Drying Apparatus, manufactured by Tokyo Ohka Kogyo Co., Ltd.), a part of the solvent was dried in 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C for 3 minutes to obtain a film thickness of 2.4 μm black photosensitive composition layer.

利用具有超高壓水銀燈的近接型曝光機(日立高新電子工程(Hitachi High-Tech Electronics Engineering)(股)公司製造)，在將基板與遮罩(具有影像圖案的石英曝光遮罩)垂直豎立的狀態下，將曝光遮罩面與該感光性組成物層之間的距離設定為200 μm，以曝光量300 mJ/cm2進行圖案曝光。 A state in which a substrate and a mask (a quartz exposure mask having an image pattern) are vertically erected by a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp Next, the distance between the exposure mask surface and the photosensitive composition layer was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ/cm 2 .

繼而，利用噴淋噴嘴來噴霧純水，使該黑色感光性組成物層的表面均勻潤濕後，利用KOH系顯影液(含有KOH、非離子界面活性劑，商品名：CDK-1，富士膠片電子材料(FUJIFILM Electronic Materials)公司製造)，以23℃、80秒、扁平噴嘴壓力為0.04 MPa的條件進行噴淋顯影而獲得圖案化影像。繼而，利用超高壓清洗噴嘴，以9.8 MPa的壓力噴射超純水來進行殘渣去除。最後在220℃下進行30分鐘熱處理，形成黑色矩陣。 Then, the pure water is sprayed by a shower nozzle to uniformly wet the surface of the black photosensitive composition layer, and then a KOH-based developing solution (containing KOH, a nonionic surfactant, trade name: CDK-1, Fujifilm) is used. The electronic material (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was spray-developed under the conditions of 23 ° C, 80 seconds, and a flat nozzle pressure of 0.04 MPa to obtain a patterned image. Then, ultra-pure water was sprayed at a pressure of 9.8 MPa using an ultra-high pressure washing nozzle to carry out residue removal. Finally, heat treatment was carried out at 220 ° C for 30 minutes to form a black matrix.

〈RGB畫素的形成〉 <Formation of RGB pixels>

於形成有上述黑色矩陣的玻璃基板上，以與黑色矩陣形成時相同的步驟，對紅色感光性組成物R、藍色感光性組成物B、 實施例1-1中製作的綠色著色感光性組成物分別依次進行積層以及圖案化，獲得RGB3色畫素的彩色濾光片。此時，RGB各種顏色的著色部膜厚為1.6 μm。 On the glass substrate on which the black matrix is formed, the red photosensitive composition R, the blue photosensitive composition B, and the same steps as in the case of forming the black matrix The green colored photosensitive composition produced in Example 1-1 was sequentially laminated and patterned to obtain a color filter of RGB 3 color pixels. At this time, the thickness of the coloring portion of each of the RGB colors was 1.6 μm.

〈氧化銦錫(indium tin oxide，ITO)電極的形成〉 <Formation of Indium Tin Oxide (ITO) Electrode>

將形成有彩色濾光片的玻璃基板放入至濺鍍裝置中，在100℃下全面真空蒸鍍1300 Å厚度的ITO後，在240℃下進行90分鐘退火而使ITO結晶化，形成ITO透明電極。 The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and 1300 Å thick ITO was vacuum-deposited at 100 ° C, and then annealed at 240 ° C for 90 minutes to crystallize ITO to form ITO transparent. electrode.

〈間隔件的形成〉 <Formation of spacers>

以與日本專利特開2004-240335號公報的[實施例1]中記載的間隔件形成方法相同的方法，在上述所製作的ITO透明電極上形成間隔件。 A spacer is formed on the ITO transparent electrode produced as described above in the same manner as the method of forming a spacer described in [Example 1] of JP-A-2004-240335.

〈液晶配向控制用突起的形成〉 <Formation of protrusions for liquid crystal alignment control>

使用下述正型感光性樹脂層用塗佈液，在上述形成有間隔件的ITO透明電極上形成液晶配向控制用突起。 A liquid crystal alignment control projection is formed on the ITO transparent electrode on which the separator is formed by using the following coating liquid for a positive photosensitive resin layer.

其中，曝光、顯影、及烘烤步驟使用以下方法。 Among them, the exposure, development, and baking steps use the following methods.

以規定的光罩自感光性樹脂層的表面起成為100 μm的距離的方式配置近接曝光機(日立高新電子工程股份有限公司製造)，隔著該光罩，利用超高壓水銀燈以照射能量150 mJ/cm2進行近接(proximity)曝光。 A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) was placed so as to have a distance of 100 μm from the surface of the photosensitive resin layer in a predetermined mask, and the irradiation energy was 150 mJ by using an ultrahigh pressure mercury lamp through the mask. /cm 2 performs proximity exposure.

繼而，一邊利用噴淋式顯影裝置，將2.38%四甲基氫氧化銨水溶液在33℃下對基板噴霧30秒，一邊進行顯影。如此，藉 由將感光性樹脂層的不需要部分(曝光部)顯影去除，而獲得在彩色濾光片側基板上形成有液晶配向控制用突起的液晶顯示裝置用基板，該液晶配向控制用突起包含經圖案化為所需形狀的感光性樹脂層。 Then, while developing the substrate by spraying a 2.38% tetramethylammonium hydroxide aqueous solution at 33 ° C for 30 seconds by a shower type developing device. So, borrow By developing and removing an unnecessary portion (exposure portion) of the photosensitive resin layer, a substrate for a liquid crystal display device in which a projection for liquid crystal alignment control is formed on a color filter side substrate is obtained, and the projection for liquid crystal alignment control includes a pattern The photosensitive resin layer is formed into a desired shape.

繼而，藉由將該形成有液晶配向控制用突起的液晶顯示裝置用基板在230℃下烘烤30分鐘，而在液晶顯示裝置用基板上形成經硬化的液晶配向控制用突起。 Then, the substrate for a liquid crystal display device in which the liquid crystal alignment control projections were formed was baked at 230 ° C for 30 minutes to form a cured liquid crystal alignment control projection on the liquid crystal display device substrate.

[正型感光性樹脂層用塗佈液配方] [Formulation of Coating Solution for Positive Photosensitive Resin Layer]

．正型抗蝕劑液(富士膠片電子材料(股)公司製造的FH-2413F) 53.0份 . Positive resist liquid (FH-2413F manufactured by Fujifilm Electronic Materials Co., Ltd.) 53.0 parts

．甲基乙基酮 46.5份 . Methyl ethyl ketone 46.5 parts

．Megafac F-780F(DIC(股)公司製造) 0.05份 . Megafac F-780F (manufactured by DIC) 0.05 parts

〈液晶顯示裝置的製作〉 <Production of Liquid Crystal Display Device>

在上述所得的液晶顯示裝置用基板上進而設置包含聚醯亞胺的配向膜。然後，在相當於黑色矩陣外框的位置印刷環氧樹脂的密封劑，該黑色矩陣外框是以包圍彩色濾光片的畫素群的方式設置於周圍，同時滴下MVA模式用液晶，貼合對向基板後，對所貼合的基板進行熱處理而使密封劑硬化。 Further, an alignment film containing polyimine is further provided on the substrate for a liquid crystal display device obtained above. Then, an encapsulant of an epoxy resin is printed at a position corresponding to the outer frame of the black matrix, and the black matrix outer frame is provided around the pixel group surrounding the color filter, and the liquid crystal for MVA mode is dropped and bonded. After the counter substrate, the bonded substrate is subjected to heat treatment to cure the sealant.

於以上述方式獲得的液晶單元的兩面，貼附(股)三立(Sanritsu)公司製造的偏光板HLC2-2518。繼而，將LED光源(索尼(SONY)公司製造的液晶電視，KDL-40ZX1的背光源光源) 作為光源而配置於設置有上述偏光板的液晶單元的成為背面之側，製成液晶顯示裝置(LCD)。 On both sides of the liquid crystal cell obtained in the above manner, a polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached. Then, the LED light source (the LCD TV made by Sony (SONY), the backlight source of KDL-40ZX1) As a light source, the liquid crystal cell in which the above-mentioned polarizing plate is provided is disposed on the side of the back surface to form a liquid crystal display device (LCD).

以上述方式製成的液晶顯示裝置具有高的對比度及亮度，適合作為顯示裝置。此外，本實施例中進行了MVA模式液晶顯示裝置的評價，但認為藉由在其他模式的液晶顯示裝置、或有機EL(Organic Electro-Luminescence)顯示器的彩色濾光片中使用本發明的著色感光性組成物，亦同樣獲得良好的畫質。 The liquid crystal display device produced in the above manner has high contrast and brightness and is suitable as a display device. Further, in the present embodiment, the evaluation of the MVA mode liquid crystal display device was carried out, but it is considered that the color sensitization of the present invention is used in the color filter of the liquid crystal display device of another mode or the organic EL (Organic Electro-Luminescence) display. Sexual compositions also receive good picture quality.

[實施例2-1] [Example 2-1]

將下述各成分混合、溶解，來製備著色感光性組成物2-1，進行評價。 The colored photosensitive composition 2-1 was prepared by mixing and dissolving each of the following components, and the evaluation was performed.

．有機溶劑：丙二醇單甲醚乙酸酯 21份 . Organic solvent: propylene glycol monomethyl ether acetate 21 parts

．有機溶劑：二乙二醇乙基甲醚 25份 . Organic solvent: diethylene glycol ethyl methyl ether 25 parts

．鹼可溶性樹脂1：甲基丙烯酸烯丙酯/甲基丙烯酸共聚物=莫耳比70/30(重量平均分子量26800) 1份 . Alkali-soluble resin 1: allyl methacrylate / methacrylic acid copolymer = molar ratio 70 / 30 (weight average molecular weight 26800) 1 part

．嵌段異氰酸酯B1 2.2份 . Block isocyanate B1 2.2 parts

．聚合性化合物：單體M1(東亞合成(股)製造的M215，下述結構) 3.3份 . Polymerizable compound: monomer M1 (M215 manufactured by East Asia Synthetic Co., Ltd., the following structure) 3.3 parts

．聚合性化合物：日本化藥(股)製造，KAYARAD DPHA 3.2份 . Polymeric compound: manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA 3.2 parts

．聚合抑制劑：對甲氧基苯酚 0.003份 . Polymerization inhibitor: p-methoxyphenol 0.003 parts

．光聚合起始劑1：1-(O-乙醯基肟)-1-[9-乙基-6-(硫苯醯 基)-9H-咔唑-3-基]丙酮 0.4份 . Photopolymerization initiator: 1-(O-ethylindenyl)-1-[9-ethyl-6-(thiophenylhydrazine) Base)-9H-carbazol-3-yl]acetone 0.4 parts

．多官能硫醇化合物：昭和電工(股)製造的Karenz MTBD1 0.4份 . Polyfunctional thiol compound: 0.8 parts of Karenz MTBD1 manufactured by Showa Denko Co., Ltd.

．密接改良劑：3-甲基丙烯醯氧基丙基三甲氧基矽烷 0.15份 . Adhesive improver: 3-methylpropenyloxypropyltrimethoxydecane 0.15 parts

．氟系界面活性劑：DIC公司製造的Megafac F-554(0.2%丙二醇單甲醚乙酸酯溶液) 5.5份 . Fluorine-based surfactant: Megafac F-554 (0.2% propylene glycol monomethyl ether acetate solution) manufactured by DIC Corporation 5.5 parts

．綠色分散組成物1 30份 . Green dispersion composition 1 30 parts

[實施例2-2~實施例2-6] [Example 2-2 to Example 2-6]

著色感光性組成物2-1的製備中，將綠色分散組成物1中所含的染料Y1變更為染料Y2~染料Y6，除此以外，以與著色感光性組成物2-1的製備相同的方式製作著色感光性組成物2-2~著色感光性組成物2-6。 In the preparation of the coloring photosensitive composition 2-1, the dye Y1 contained in the green dispersion composition 1 is changed to the dye Y2 to the dye Y6, and the preparation is the same as that of the coloring photosensitive composition 2-1. In the manner of coloring photosensitive composition 2-2 to coloring photosensitive composition 2-6.

使用著色感光性組成物2-1~著色感光性組成物2-6，以 如下方式進行評價。將結果示於表2中。 Using the coloring photosensitive composition 2-1 to the coloring photosensitive composition 2-6, Evaluation was performed as follows. The results are shown in Table 2.

〈相對介電常數〉 <Relative permittivity>

相對介電常數是利用下述a)~i)的方法來進行。 The relative dielectric constant is carried out by the following methods a) to i).

a)於鉻包覆玻璃基板(1邊為75 mm，鉻膜的厚度為0.3 μm)上，以硬化後(後烘烤後)的膜厚成為3.2 μm的方式調整轉速，利用旋轉塗佈機來塗佈著色感光性組成物。 a) Adjust the rotation speed on a chrome-coated glass substrate (75 mm on one side and 0.3 μm on the chrome film) so that the film thickness after hardening (post-baking) is 3.2 μm, using a spin coater The colored photosensitive composition was applied.

b)繼而，在加熱板上以100℃、120秒的條件，將形成有著色膜的鉻包覆玻璃基板進行預烤，使溶劑乾燥。 b) Next, the chromium-coated glass substrate on which the colored film was formed was prebaked on a hot plate at 100 ° C for 120 seconds to dry the solvent.

c)預烤後，使用2.5 kw的超高壓水銀燈，以50 mJ/cm2的曝光量對著色膜照射光。 c) After prebaking, the colored film was irradiated with light at a exposure amount of 50 mJ/cm 2 using a 2.5 kw ultrahigh pressure mercury lamp.

d)繼而，利用熱風循環式乾燥機，以220℃、60分鐘的條件，將形成有著色膜的鉻包覆玻璃基板進行加熱硬化(後烘烤)，製作試驗片。 d) Then, the chromium-coated glass substrate on which the colored film was formed was subjected to heat curing (post-baking) at 220 ° C for 60 minutes using a hot air circulation dryer to prepare a test piece.

e)後烘烤後，削去試驗片的一個角落的著色膜，使鉻表面露出。 e) After post-baking, the colored film at one corner of the test piece is shaved to expose the chrome surface.

f)繼而，於試驗片的背面旋轉塗佈銀漿，使其風乾。然後，利用上述銀漿使表面的鉻露出面與背面的銀漿塗佈面導通(連接)。 f) Then, the silver paste was spin-coated on the back side of the test piece and allowed to air dry. Then, the silver exposed surface of the surface is electrically connected (connected) to the silver paste coated surface on the back surface by the above silver paste.

g)乾燥後，在試驗片的表塗膜面，使用真空蒸鍍裝置(商品名：離子濺鍍E1030，日立(股)製造)，利用Pt-Pd靶材，以圖1所示的方式，在試驗片1(基板)上製作蒸鍍厚度約為50 nm 的主電極2(內圓)及保護電極3(外圓)。此外，試驗片1上露出上述e)中削去的鉻表面4。 g) After drying, a vacuum vapor deposition apparatus (trade name: ion sputtering E1030, manufactured by Hitachi Co., Ltd.) was used on the surface of the test piece, and a Pt-Pd target was used, as shown in Fig. 1, On the test piece 1 (substrate), the evaporation thickness is about 50 nm. Main electrode 2 (inner circle) and guard electrode 3 (outer circle). Further, the test piece 1 was exposed to the chrome surface 4 which was cut in the above e).

h)製作電極後，利用觸針式表面形狀測定器(商品名：DEKTAK3，(股)優貝克(ULVAC)製造)來測定試驗片的未帶有電極的部分的塗膜的厚度。 h) After the electrode was produced, the thickness of the coating film of the portion of the test piece without the electrode was measured by a stylus type surface shape measuring device (trade name: DEKTAK3, manufactured by ULVAC).

i)繼而，在電容測定器(精密阻抗分析儀4294A，安捷倫科技(Agilent Technology)(股)製造)中安裝介電試驗裝置16451B及電極，進而安裝上述g)中的試驗片，測定施加1 kHz、0.5 V的交流電壓時的相對介電常數ε'。以下述判定基準來評價測定結果。 i) Next, a dielectric tester 16451B and an electrode were mounted in a capacitance measuring device (Precision Impedance Analyzer 4294A, manufactured by Agilent Technology Co., Ltd.), and the test piece in the above g) was mounted, and the measurement was applied at 1 kHz. The relative dielectric constant ε' at an AC voltage of 0.5 V. The measurement results were evaluated on the basis of the following criteria.

(判定基準) (judgment basis)

A：相對介電常數ε'小於3.0 A: Relative dielectric constant ε' is less than 3.0

B：相對介電常數ε'為3.0以上~小於5.0 B: The relative dielectric constant ε' is 3.0 or more and less than 5.0.

C：相對介電常數ε'為5.0以上 C: relative dielectric constant ε' is 5.0 or more

〈耐剝離液性〉 <Release resistance>

以如下順序a)~e)測定試驗片的膜厚度，算出膨潤率，將其算出值作為評價耐剝離液性的指標。但，耐剝離液性差的試驗片有在浸漬於剝離液中時塗膜溶解於剝離液中、或從基板上剝落而無法測定膜厚的試驗片。此種試驗片評價為「×」。 The film thickness of the test piece was measured in the following order a) to e), and the swelling ratio was calculated, and the calculated value was used as an index for evaluating the peeling resistance. However, the test piece which is inferior in peeling liquid property has the test piece which melt|dissolved in the peeling liquid, or peeling from a board|substrate, and can not measure the film thickness, when it is immersed in the peeling liquid. Such a test piece was evaluated as "x".

a)測定藉由上述[相對介電常數的測定]的d)而獲得的試驗片的膜厚(FT0)。 a) The film thickness (FT0) of the test piece obtained by d) of the above [measurement of relative dielectric constant] was measured.

b)測定後，使用單乙醇胺(MEA)與二甲基亞碸(DMSO)的混合物(MEA/DMSO=7/3質量比)作為剝離液，將上述試驗片在剝離液中以80℃浸漬120秒。 b) After the measurement, a mixture of monoethanolamine (MEA) and dimethyl hydrazine (DMSO) (MEA/DMSO = 7/3 by mass) was used as a stripping solution, and the above test piece was immersed in a stripping solution at 80 ° C. second.

c)於槽中裝滿MEA/DMSO=7/3的溶液，將上述b)的浸漬後的試驗片進一步浸漬，然後，在觸針式表面形狀測定器(商品名：DEKTAK3，(股)優貝克製造)的試驗片支持台上載置由剝離液覆蓋表面的狀態的試驗片，測定塗膜厚度(FT1)(利用剝離液的膨潤狀態的膜厚測定)。 c) The tank is filled with a solution of MEA/DMSO=7/3, and the impregnated test piece of the above b) is further immersed, and then, in a stylus type surface shape measuring device (trade name: DEKTAK3, (share) excellent A test piece in a state in which the surface was covered with a peeling liquid was placed on the test piece support table of Baker's manufacture, and the film thickness (FT1) (measurement of the film thickness by the swelling state of the peeling liquid) was measured.

d)於另一槽中裝滿純水，浸漬上述c)中膨潤的試驗片，靜置1晚，將塗膜中所含的剝離液置換為水後，將試驗片在200℃下乾燥30分鐘，再次測定塗膜厚度(FT2)。 d) The other tank is filled with pure water, and the test piece swollen in the above c) is immersed, left to stand for 1 night, and the peeling liquid contained in the coating film is replaced with water, and then the test piece is dried at 200 ° C. In minutes, the film thickness (FT2) was measured again.

e)使用藉由上述而測定的FT0、FT1、FT2，由下述式算出試驗片的膨潤率及膜減少率，基於下述基準來評價耐剝離液性。此外，由於(FT1-FT0)是測定藉由剝離液的表觀膨潤，故而由經剝離液侵蝕的膜減少部分(FT2-FT0)進行修正，算出真正的膨潤率。以下述判定基準來評價測定結果。 e) Using the FT0, FT1, and FT2 measured by the above, the swelling ratio and the film reduction rate of the test piece were calculated from the following formula, and the peeling resistance was evaluated based on the following criteria. Further, since (FT1-FT0) measures the apparent swelling by the peeling liquid, the film-reduced portion (FT2-FT0) eroded by the peeling liquid is corrected to calculate the true swelling ratio. The measurement results were evaluated on the basis of the following criteria.

真正的膨潤率(%)=100×(FT1-FT2)/FT0 The true swelling rate (%) = 100 × (FT1-FT2) / FT0

膜減少率(%)=100×(FT2-FT0)/FT0 Membrane reduction rate (%) = 100 × (FT2-FT0) / FT0

(判定基準) (judgment basis)

A：真正的膨潤率≦40%，且膜減少率≦5%，耐剝離液性良好。 A: The true swelling ratio is 40%, and the film reduction rate is 5%, and the peeling resistance is good.

B：真正的膨潤率≦40%，且膜減少率>5%，耐剝離液性在容許的範圍內。 B: The true swelling ratio is %40%, and the film reduction rate is >5%, and the peeling resistance is within an allowable range.

C：塗膜溶解或者剝離，耐剝離液性差。 C: The coating film is dissolved or peeled off, and the peeling resistance is poor.

可知，由本發明的特定染料的組合所形成的著色感光性組成物即便用於COA用途的彩色濾光片，亦表現出適宜的性能。 It is understood that the colored photosensitive composition formed by the combination of the specific dyes of the present invention exhibits appropriate performance even in a color filter used for COA use.

1‧‧‧試驗片 1‧‧‧Test piece

2‧‧‧主電極 2‧‧‧Main electrode

3‧‧‧保護電極 3‧‧‧Protective electrode

4‧‧‧鉻表面 4‧‧‧Chromium surface

Claims (13)

一種著色感光性組成物，包含：(A)綠色顏料、(B)具有與上述綠色顏料不同的母骨架的染料、以及(C)聚合性化合物，並且上述(B)染料的15質量%以上吸附於上述(A)綠色顏料的表面。 A colored photosensitive composition comprising: (A) a green pigment, (B) a dye having a parent skeleton different from the green pigment, and (C) a polymerizable compound, and the (B) dye is adsorbed at 15% by mass or more On the surface of the above (A) green pigment. 如申請專利範圍第1項所述的著色感光性組成物，其中包含：將上述(A)綠色顏料與上述(B)染料在同一系統內進行分散處理而獲得的分散組成物。 The colored photosensitive composition according to claim 1, which comprises a dispersion composition obtained by dispersing the (A) green pigment and the (B) dye in the same system. 如申請專利範圍第2項所述的著色感光性組成物，其中上述分散組成物是當將分散初期的分散組成物中的上述(B)染料的濃度設為Ci，且將分散結束後的分散組成物中的上述(B)染料的濃度設為Cf時，滿足Ci>Cf的關係的分散組成物。 The coloring photosensitive composition according to the second aspect of the invention, wherein the dispersion composition is a dispersion of the dye (B) in the dispersion composition at the initial stage of dispersion, and is dispersed after the dispersion is completed. When the concentration of the above (B) dye in the composition is Cf, the dispersion composition satisfying the relationship of Ci>Cf. 如申請專利範圍第1項所述的著色感光性組成物，其中上述(B)染料是選自下述通式(a-1)、通式(a-2)、通式(b)以及通式(c)所組成組群中的至少一者所表示的化合物： 通式(a-1)及通式(a-2)中，R1~R5分別獨立地表示氫原子、或者一價取代基； 通式(b)中，R6及R7分別獨立地表示氫原子、或者一價取代基；R8表示氫原子、脂肪族基、芳基、雜環基、胺甲醯基、烷氧基羰基、芳氧基羰基、醯基、烷基磺醯基、芳基磺醯基、或者胺磺醯基；Q表示重氮成分殘基；通式(b)所表示的色素可在任意位置形成二聚物以上的多聚物； 通式(c)中，R9及R10分別獨立地表示氫原子、或者一價取代基；R11表示氫原子、脂肪族基、芳基、雜環基、胺甲醯基、烷氧基羰基、芳氧基羰基、醯基、烷基磺醯基、芳基磺醯基、或者胺磺醯基，A表示重氮成分殘基。 The colored photosensitive composition according to claim 1, wherein the dye (B) is selected from the group consisting of the following formula (a-1), formula (a-2), formula (b), and a compound represented by at least one of the groups consisting of formula (c): In the general formula (a-1) and the general formula (a-2), R 1 to R 5 each independently represent a hydrogen atom or a monovalent substituent; In the formula (b), R 6 and R 7 each independently represent a hydrogen atom or a monovalent substituent; and R 8 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an amine formazan group, an alkoxy group. a carbonyl group, an aryloxycarbonyl group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group; Q represents a diazo component residue; the pigment represented by the formula (b) can be formed at any position a polymer of a dimer or more; In the formula (c), R 9 and R 10 each independently represent a hydrogen atom or a monovalent substituent; and R 11 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an amine formazan group, an alkoxy group. A carbonyl group, an aryloxycarbonyl group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group, or an aminesulfonyl group, and A represents a diazo component residue. 如申請專利範圍第1項所述的著色感光性組成物，其中包含：將上述(A)綠色顏料與上述(B)染料預混合後，將所得的有色材料混合物分散而獲得的分散組成物。 The colored photosensitive composition according to claim 1, which comprises a dispersion composition obtained by preliminarily mixing the green pigment (A) and the dye (B), and dispersing the obtained colored material mixture. 如申請專利範圍第1項所述的著色感光性組成物，其中更含有(D)光聚合起始劑。 The colored photosensitive composition according to claim 1, which further comprises (D) a photopolymerization initiator. 如申請專利範圍第1項所述的著色感光性組成物，其中更含有(E)鹼可溶性黏合劑。 The colored photosensitive composition according to claim 1, further comprising (E) an alkali-soluble binder. 一種彩色濾光片，其是使用如申請專利範圍第1項至第7項中任一項所述的著色感光性組成物來製作。 A color filter produced by using the colored photosensitive composition according to any one of claims 1 to 7. 一種彩色濾光片的製造方法，包括：著色層形成步驟，將如申請專利範圍第1項至第7項中任一項所述的著色感光性組成物塗佈於支持體上而形成著色層；曝光步驟，將所形成的著色層曝光成圖案式樣；以及顯影步驟，將曝光後的著色層進行顯影而形成著色圖案。 A method of producing a color filter, comprising: a colored layer forming step of applying a colored photosensitive composition according to any one of claims 1 to 7 to a support to form a colored layer And an exposing step of exposing the formed coloring layer to a pattern pattern; and developing a step of developing the exposed coloring layer to form a colored pattern. 一種顯示裝置，包括利用如申請專利範圍第8項所述的彩色濾光片而獲得的彩色濾光片。 A display device comprising a color filter obtained by using the color filter of claim 8 of the patent application. 一種顯示裝置，包括利用如申請專利範圍第9項所述的 製造方法而獲得的彩色濾光片。 A display device comprising using the method as recited in claim 9 A color filter obtained by the manufacturing method. 一種著色感光性組成物的製造方法，其將(A)綠色顏料、(B)具有與上述綠色顏料不同的母骨架的染料進行分散而製備分散組成物，然後使用上述分散組成物來製備著色感光性組成物。 A method for producing a colored photosensitive composition, which comprises (A) a green pigment, (B) a dye having a parent skeleton different from the above green pigment, to prepare a dispersion composition, and then using the above dispersion composition to prepare a coloring photosensitive Sexual composition. 一種著色感光性組成物的製造方法，其將(A)綠色顏料、(B)具有與上述綠色顏料不同的母骨架的染料進行混合而製備有色材料組成物，將上述有色材料組成物分散來製備分散組成物，然後使用上述分散組成物來製備著色感光性組成物。 A method for producing a colored photosensitive composition, which comprises (A) a green pigment and (B) a dye having a parent skeleton different from the green pigment to prepare a colored material composition, and dispersing the colored material composition to prepare The composition was dispersed, and then the above-mentioned dispersion composition was used to prepare a colored photosensitive composition.
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